Methods and devices for evaluating the contents of materials

ABSTRACT

Methods for determining the hardness and/or ductility of a material by compression of the material are provided as a first aspect of the invention. Typically, compression is performed on multiple sides of a geologic material sample in a contemporaneous manner. Devices and systems for performing such methods also are provided. These methods, devices, and systems can be combined with additional methods, devices, and systems of the invention that provide for the analysis of compounds contained in such samples, which can indicate the presence of valuable materials, such as petroleum-associated hydrocarbons. Alternatively, these additional methods, devices, and systems can also stand independently of the methods, devices, and systems for analyzing ductility and/or hardness of materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of PCT/US2017/065921, filed Dec. 12,2017 entitled Methods and Devices for Evaluation the Contents ofMaterials which claims the benefit of U.S. Provisional Application No.62/434,399, filed Dec. 14, 2016, entitled Methods and Devices forEvaluating the Contents of Materials, the entirety of each of whichbeing hereby incorporated by reference.

FIELD OF THE INVENTION

This invention pertains to novel methods of evaluating the contents ofmaterials, including, for example, volatile substances such aspetroleum-related hydrocarbons in geological materials, as well asdevices that can be used in the practice of the methods and otherapplications.

BACKGROUND OF THE INVENTION

Human evaluation of the content of materials has probably been practicedfor longer than any written records. However, the ability to useinformation associated with a material to understand the properties ofassociated materials, such as surrounding geologic formations, has beenlargely developed in the last 100 years, beginning with the Schlumbergerbrothers' discovery that electric resistivity could be used to evaluatethe structure and likely content of geologic structures, and thusprovide a mechanism for finding subsurface materials, such as fossilfuel deposits. While a significant advance, resistivity has proven to beof limited utility, especially in modern times in which easy to findpetroleum and natural gas deposits are increasingly more difficult todetect with such technology.

Prior technology involving the analysis of rock materials, such as todetermine the presence of hydrocarbons in a geologic formation, havefocused on the analysis of material in fluid inclusions. Fluidinclusions are often characterized as “bubbles” of fluid trapped withina host material, such as rock. These compartments within rock or othermaterial are usually very small, from 1 to 20 microns across. Fluidinclusions are characterized by being completely sealed and isolatedfrom the environment, typically over very long period of time (on ageologic scale—e.g., over millions of years). The contents of fluidinclusions are believed to be the remnants of the exact fluid associatedwith the rock material at formation. As such, the content of inclusionscan provide information about the fluid composition, temperature andpressure at which a material was formed and what it may contain.

In one type of typical fluid inclusion analyses, a rock sample, usuallyfrom a sedimentary rock, is crushed under strong vacuum and the trappedfluids that are released from the crushing are analyzed, such as with amass spectrometer. Prior to my inventions described herein, theconditions under which mass spectrometers operate have dictated how thedevices and methods for fluid inclusion analysis have been performed.Fluid inclusion materials have shown some usefulness in the discovery ofhydrocarbon materials and today is a commonly practiced method performedon materials obtained from oil well drilling. However, fluid inclusionanalysis also is of limited utility due to a number of issues, such asthe content of the inclusion often not matching the present-day fluidsin the geologic formation.

Specific patents describing my prior inventions, the inventions of myco-inventors, and other inventors include U.S. Pat. No. 4,960,567, whichrelates to a method for obtaining gasses from fluid inclusions foranalysis through mass spectrometry and U.S. Pat. No. 5,241,859, whichdescribes a method in which material from a collection of fluidinclusions are analyzed to identify collections that are rich inhydrocarbons, which can then be further analyzed, such as through massspectrometry analysis. U.S. Pat. No. 5,328,849 describes methods formapping subsurface formations by analyzing fluid inclusions in severalsamples through specialized devices I also invented.

U.S. Pat. No. 6,661,000 describes an invention made by me and myco-inventors wherein we invented a method for analyzing surface and poreliquids, as opposed to fluid inclusions, by a method in which cuttingsor other samples are subjected directly to mass spectrometry analysisunder high vacuum. However, one of the shortcomings with that method isthe loss of gasses associated with the sample due to the need to applysuch relatively high vacuum levels in order to make the devices weinvented operate.

The invention provides methods and devices that not only address thelimitations of these prior inventions but also greatly expand on them interms of the applicability of methods to various materials andassociated materials, extending well beyond simple analysis of potentialhydrocarbon-associated rock samples. These and other advantages of theinvention, as well as additional inventive features, will be apparentfrom the description of the invention provided herein.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides new methods for determiningthe ability to subject a geologic material to fracking and similarprocesses in which the hardness and/or ductility of a material isdetermined by compression of one or more samples of the material,especially on multiple sides of the sample in a contemporaneous manner.The sample is typically associated with a drill operation and often is acutting. The methods typically comprise analysis of many samples, suchas 5, 10, 15, 20, 30, 40, 50, or more samples (e.g., 100, 250, 500, 750,1,000, 1,250, 1,500, or more samples), usually from different locationswith respect to most of the other analyzed samples (such as beingseparated by at least 0.75 vertical and/or horizontal feet). Theinvention further provides devices and systems for performing suchmethods of the first aspect.

These methods, devices, and systems can be combined with additionalmethods, devices, and systems of the invention that provide for theanalysis of volatile substances contained in such samples, such ascuttings, which can indicate the presence of substances in the materialassociated with the sample, such as petroleum-associated hydrocarbons(oil and/or gas). Alternatively, such additional methods, devices, andsystems can also stand independently of the methods, devices, andsystems for analyzing ductility and/or hardness of materials of thefirst aspect of the invention, as a second, independent aspect of theinvention. The method of the second aspect typically comprises exposingthe samples to one or more forces that allow or promote the release ofthe volatile substances, capturing the volatile substances, and thenanalyzing the volatile substances, so as to identify the nature of thecomposition of the material. Such methods often comprise application ofa gentle force, such as a gentle vacuum step (e.g., at about 10-about100 millibars), which allows for capture of volatile fluids in thesample without significant loss of such materials in the analyticalmethod.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representation of an illustrative device/system of theinvention for analyzing both the compressibility of samples and thevolatile substance content of such samples through a non-selective trapof condensable gasses, a separate trap of non-condensable gasses, andmass spectrometry analysis of such compounds.

FIG. 2 is an example of a data set obtained by performing methods of theinvention in connection with petroleum well-associated cuttings.

FIG. 3 provides another example of a data set obtained by performingmethods of the invention in connection with petroleum well-associatedcuttings.

FIG. 3B provides a simplified, stylized view of select data shown inFIG. 3.

FIG. 4A is an illustrative plot of oil, water, and oil saturated waterin connection with a vertically oriented petroleum well.

FIG. 4B is a simplified representation of key data provided in FIG. 4A.

FIG. 5 provides yet another example of data obtained by performingmethods of the invention on cuttings.

FIG. 5B provides a simplified representation of select data presented inFIG. 5.

FIG. 6 is a representation of a type of petroleum-associated geologicformation that can be identified and characterized by use of methods ofthe invention.

FIG. 7 provides a plot of acetic acid measurements in a geologicformation against resistivity log data to identify petroleum associatedregions in sandstone formations/sands.

FIGS. 8A and 8B provide a plot of multiple hydrocarbons at differentdepths to analyze the nature of petroleum deposits in a geologicformation.

FIG. 8C provides a stylized representation of data associated with aparticular type of geologic deposit that can be characterized by methodsof the invention.

FIG. 9 is an illustrative representation of mapping a region of sitesusing the method of the invention to characterize a larger areacomprising multiple drilling sites.

FIG. 10 is another plot of data obtained using methods of the inventionincluding hydrocarbon data, oil saturated water, and other data elementsused to identify and characterize deposits within a geologic formationat different depths.

FIG. 10A is a simplified representation of key data patterns in FIG. 10.

FIG. 11 provides a representation of two data sets for differentformations/sites that can be differentially analyzed by methods of theinvention.

FIG. 12 provides an illustration of a well site device forfrackability/compression analysis of cuttings allowing for realtime/near real time steering of a lateral well.

DETAILED DESCRIPTION OF THE INVENTION

The invention described herein provides various types of devices andmethods for analyzing the contents of hard mineral-based materials, suchas rock samples taken from geologic formations. One key use of thesemethods and devices is the analysis of the drill cuttings from petroleumwells for the contents of certain compounds in such cuttings or that canbe obtained from such cuttings, which in turn provide information aboutthe geologic material associated with the cuttings. However, the methodsand devices of the invention are not limited to such applications andsettings and can be applied to other settings, as will be discussedfurther herein.

In a primary aspect, the invention described herein provides a methodfor analyzing volatile substances in a material comprising the steps of(a) providing an analyzable sample of a material containing ananalyzable amount of one or more volatile substances, (b) permitting therelease of fluid (e.g., gas) containing the volatile substances from thematerial, (c) optionally subjecting the sample to one or more forces toaid in the release of the fluid, (e) optionally trapping the fluid bycontact with a media, in an analyzable amount (an aliquot), (d)optionally isolating the fluid from the material, (e1) applying energyor one or more forces to the aliquot so as to cause volatile compoundsin the aliquot, if present, to form other chemical substances(energy-treated gas(ses)) in a predictable manner and/or (e2) releasingvolatile substances from the aliquot as trap-released fluids in apredictable sequence, and (f) analyzing the chemistry of one or moretrap-released fluids and/or energy-treated fluids.

The inventive methods described herein can be practiced with anysuitable material containing any suitable number and/or suitable numberof any suitable type of volatile substances. Suitability in this respectmeans that the volatile substances are amenable to analysis by themethods and/or devices of the invention, which can be determined by theprinciples described here or through application of routineexperimentation. A volatile substance in the context of the invention isa material that will take the form of a gas under the conditions inwhich the method is performed. Conditions relevant to whether a materialis in the form of a gas at a particular time include the pressure thematerial is under at the time. In one aspect of the invention, at leastone volatile substance is released from the material at atmosphericpressure. In another aspect, at least one volatile material analyzed bythe method is released from the material under a vacuum (a pressurelower than atmospheric pressure—i.e., a pressure of less than about 760Torr or 1.013×10⁵ Pa) or significantly more of the material is releasedunder a vacuum than at atmospheric pressure (such as at least about 2times, at least about 3 times, at least about 5 times, at least about 10times, at least about 20 times, at least about 30 times, at least about50 times, or at least about 100 times atmospheric pressure).

In a particular aspect, the method includes analyzing at least onevolatile substance that is released from the material under low vacuumconditions. Low vacuum conditions mean pressure conditions ranging fromabout 760 to about 25 Torr or 1×10⁵ to 3×10³ Pa (in this document eachdisclosure of a quantity modified by modifiers such as “about” is to beconstrued as simultaneously providing the corresponding exact disclosureand each disclosure of a range is to be construed as disclosing eachunit of the same order of magnitude as the end points of the range,e.g., a disclosure of the range of 1-5 also is to be construed asdisclosing the numbers 1, 2, 3, 4, and 5 individually). In anotherexemplary aspect, the method includes the step of analyzing at least onevolatile substance that is released at under but close to 1000millibars, such as about 40 millibars to about 950 millibars, e.g.,about 50 millibars to about 900 millibars, about 100 millibars to about800 millibars, such as about 150 millibars to about 750 millibars, orany combination of such low and high-end points.

In another context, the method also or alternatively includes analyzingat least one volatile substance that is released from the material undermedium vacuum conditions. Medium vacuum conditions mean pressures ofabout 25 Torr to about 1×10⁻³ Torr (3×10³ to 1×10⁻¹ Pa). In anotheraspect, the method includes analyzing at least one volatile substancethat is released from the material under a pressure of about 50millibars (e.g., applying one more pressures of about 20-80 millibars,such as about 30-70 millibars) and still another aspect the methodcomprises performing an analysis on an aliquot obtained by extraction atone or more pressures in the range of about 30 millibars to about 10millibars, such as about 25 millibars to about 12 millibars, e.g., about20 millibars to about 15 millibars, or any other combination of such lowand high end points.

In another aspect, the invention also includes analyzing at least onevolatile substance that is released from the material under high vacuumconditions. High vacuum conditions mean about 1×10⁻³ to about 1×10⁻⁹Torr (1×10⁻¹ to 1×10⁻⁷ Pa). In another respect, the invention includesanalyzing at least one volatile substance released under vacuumpressures of less than about 5 millibars, such as less than about 2millibars, such as less than 1 millibar. For example, in another aspect,the invention comprises analyzing at least one volatile substancereleased under vacuum pressures of about 1×10⁻² millibars or less, suchas about 1×10⁻³ to about 1×10⁻⁹ millibars.

In still other aspects of the invention, the method does not compriseapplication of high vacuum (such as those described above), which in onerespect distinguishes such aspects of this invention from prior artmethods which include or are dependent upon the application of highvacuum to perform analysis of materials. In still other aspects, thepractice of the method of the invention lacks application of either anyhigh vacuum or any medium vacuum in the release of volatile compounds.This distinguishes these aspects, among other things, from prior artmethods, such as many forms of fluid inclusion analysis, which typicallyrequire application of high vacuum and/or medium vacuum.

The material also can be any material which can be suitably subjected tothe methods of the invention. In one typical context the material is ageologic material, such as rock material, a mud, or a soil, or adrilling byproduct, especially drilling mud or a drill cutting. In thecontext of this invention terms such as “cuttings” and “drill cuttings”means rock fragments that are brought to the surface in a drillingoperation (such terms are generally understood in the art). Typically,drill cuttings are rocks that are maintained separated from drill mudsin a shaker table operation or similar separation process. Drillcuttings can have any suitable size. The size of cuttings produced at awell will depend on several factors including the geologic materialbeing drilled through and the drill bit used, with more modern drillbits often forming smaller cuttings. Particle sizes of cuttings can be,for example, as small as about 5 microns (e.g., about 10 microns orlarger, about 20 microns or larger, about 25 microns or larger, about 50microns or larger, etc.), but typically the cuttings will have particlesizes of at least about 100 microns, such as at least about 150 microns,or at least about 200 microns (e.g., about 250 microns or greater), andmay be significantly larger, such as up to about 7.5 mm (e.g., about 6.5mm or less, about 6 mm or less, or about 5 mm or less). Commonly,cuttings that typically have a particle size of between about 0.5 mm toabout 1 mm and about 5 mm to about 6 mm are used in methods of theinvention. However, in a particularly unexpected aspect of the invention(as exemplified elsewhere herein) the method has been performed usingvery small cuttings that were produced in a coring process, which aresignificantly smaller in size than typical cuttings obtained in oilproduction or exploration. Thus, for example, the method can beperformed with cuttings of about 100 microns to about 5 mm, about 50microns to about 10 mm, about 25 microns to about 7 mm, about 25 micronsto about 12.5 mm, about 50 microns to about 6.5 mm, about 0.2 mm toabout 6 mm, about 0.25 mm to about 5 mm, or about 0.5 mm to about 5 mm.These are exemplary ranges, and these endpoints of any one of theseranges can be interchanged with end points of any other range to createother suitable ranges in which to focus other exemplary methods of theinvention.

“Drilling mud”, “muds”, or “drilling fluid” in the context of thisinvention refers to a material that is distinguished from cuttings.Drilling mud is material that is at least initially introduced to a wellsite and used by the operator of a drilling operation to perform one ormore functions including providing hydrostatic pressure to preventformation fluids from entering into the well bore, maintaining thetemperature and/or “cleanliness” of the drill bit (or at leastpreventing overheating and/or obstruction), maintaining the structuralintegrity of the bore hole, and/or aiding in the carrying out of drillcuttings. Drilling muds commonly will contain materials such asbentonite, barite, or hematite and can be water-based or oil-based. Mudsoften are dense materials and thixotropic, meaning that they become morefluid with application of agitation. The nature of drilling muds and thedifferences between drilling muds and cuttings will be understood bythose skilled in the art.

In a specific context, the material is rock or mud material that isassociated with either exploratory drilling or production drilling forpetroleum, natural gas, or related materials, however materials obtainedfrom other activities such as exploratory and production drilling foreconomic mineral deposits and geothermal energy also or alternativelycould be used in practicing the methods of the invention. The materialalso or alternatively can be from other sources than from naturalgeologic formations or other non-petroleum-related geologic samples, oreven biological samples such as teeth, bones, and the like (e.g., foodor biomass from any type of living organism whether viable ornon-viable). In this respect, the methods of the invention may haveapplication in various forensic and/or intelligence applications, fordetermining the impact of processes on materials, the historical sourceor modulation of materials, and/or, for example, the origin of materialsor other information about the nature of such materials. For example, inanother context the material is construction material, such as materialused in building of commercial buildings, bridges, roads, constructionsites, antiquities, and the like. The methods also can be applied toother man-made materials such as ceramics and other types of materialsused in the manufacture or construction of other devices and structures,such as semiconductors.

In one aspect of the invention, the samples selected for analysis in theperformance of the method comprise, are substantially comprised of(i.e., more than about 20% of the samples are), are primarily comprisedof (i.e., more than 51% of the samples are), consist essentially of (arecomprised of to a level that the amount of non-conforming material doesnot impact the nature of the total sample or sample set), or consistentirely of, material that substantially lack relevant fluid inclusions(“RFIs”). “Relevant fluid inclusions” or “RFIs” in the context of thisinvention refers to fluid inclusions that (1) contain one or morematerials that are indicative of the presence of a substance in thematerial (at least in the inclusions), such as petroleum orpetroleum-related substances (e.g., organic acids, hydrocarbons, and thelike, such as acetic acid) and (2) the presence of such materialsreflect the present condition of the material (in terms of the presenceof the target substance). Samples may lack relevant fluid inclusions fora number of reasons, such as relevant fluid inclusions may have neverformed in the material (e.g., shallow, unconsolidated, young sandstoneoil reservoirs in the Gulf of Mexico) or the relevant fluid inclusionsmay have been destroyed by natural and/or human processes (e.g.,meteorite impact or drilling with polycrystalline diamond compact(“PDC”) drill bits). As indicated elsewhere, often fluid inclusions willcontain ancient fluids that often do not reflect the present fluidcontent of the material. In certain cases, relatively “young” fluidinclusions can form in a material or older fluid inclusions may befilled by relatively “young” material that is present in a material.Such fluid inclusions can be classified as RFIs. Non-relevant fluidinclusions (“NFIs”) may still provide relevant information tounderstanding the material, but they are less probative with respect tothe fluid content of the material than RFIs. Substantially lacking RFIsmeans that less than 0.000005% of the volume of the sample is made up oftarget substance (e.g., petroleum) or target substance-related fluidinclusions (e.g., only about 0.05 ppm or less of the sample volume ismade up of oil or an oil-relevant substance). In some cases theinvention is practiced wherein the amount of RFIs is even less, such as0.025 ppm or less, about 0.02 ppm or less, or even about 0.01 ppm orless of the volume of the sample is made up of targetsubstance-containing or target substance-relevant fluids (in evenfurther aspects the amount of RFIs in the sample is even less such asabout 20 parts per trillion of the volume of the sample or less, about10 parts per trillion of the volume of the sample or less, about 5 partsper trillion of the volume of the sample or less, or even about 1 partsper trillion of the volume of the sample or less. In still otheraspects, the sample or some of the sample(s) analyzed contain nodetectable amount of RFI. In some cases, the sample may contain morevolume of fluid inclusions, however the fluid inclusions will be knownto not be relevant in the sense that there is information that informsthe artisan that material in the fluid inclusion is not indicative ofthe fluid content of the material (e.g., the inclusion is indicative ofthe presence of oil, but it is known from drilling that the content ofthe material reflects little to no oil being present in the material).In certain aspects, the material and/or the sample is or comprises amaterial that lacks materials that will form a sufficient amount, size,or type of inclusion to be relevant, such as many shales orunconsolidated/young sands, which commonly lack material that is hardenough to sufficiently form inclusions that can provide detectablelevels of RFIs even if the target substance is present in the material.It is important to understand that the term “target” in this and othercontexts of describing aspects of the invention can mean, but does notalways mean, a specific substance that is expected to be present or thatis sought by the analytical methods of the invention. Thus, for example,the “target” can be one or more unknown materials that are in amaterial, such as one or more substances that are included in drillcuttings or other geologic material but that have no known compositionprior to the analysis.

In another aspect of the invention, the samples analyzed and/or thematerial comprise a low number of RFIs. For example, in a particularfacet of the invention the sample is a collection of cuttings in whichless than about 20%, less than about 15%, or about 10% or less, such asabout 5% or less of the cuttings comprise RFIs.

In other aspects, materials or samples with fluid inclusions can beincluded intentionally and will be included commonly in the sampleand/or material, and, in such cases, the method optionally canadditionally comprise, as discussed below, performance of other methodson materials containing fluid inclusions taken from site and/or includedin the samples.

The material and/or samples typically will include fissures, fractures,pockets, cracks, etc., which contain target materials of interest, suchas volatile hydrocarbons. Such fissures, fractures, etc. (referredcollectively herein as “target substance pores” or “TSPs”), will oftendesirably contain target substance or target substance-relevant material(e.g., such as organic acids and/or hydrocarbons that are indicative ofthe presence of petroleum) that also in some cases are (1) present inrelevant amounts in the material (either in fluid form or are absorbedor adsorbed in the material), rather than material that are artifacts ofprior existing conditions, as is the case with many NFIs, (2) areexposed to the surrounding environment in some amount (such as by beingcontained in a pore in the material that is exposed to the surroundingenvironment) (in other words are not completely sealed off from theenvironment as is the case with fluid inclusions), or (3) can becharacterized in satisfying both (1) and (2). A “pore fluid” in thecontext of this invention means a substance that is ordinarily liquid orgas in association with the material, contains one or more volatiles,and is found in a TSP and satisfies conditions (1), (2), or (3) of thepreceding sentence. In some aspects, the invention is characterized byanalyzing one or more samples containing an analyzable amount of porefluid(s) and/or by analyzing one or more samples containing ananalyzable amount of a pore fluid-related substance.

In a set of particular aspects, the material consists of, comprises, oris substantially comprised of a geologic material that has notexperienced significant enough burial diagenesis to have formed fluidinclusions. “Substantially comprised of” in the context of thisinvention means that a substantially majority, such as at least 65%,more often at least 75%, such as at least 80%, at least 85%, at least90%, or even at least 95% of the referenced material or composition iscomprised of the component at issue. In particular aspects, the materialconsists of, is comprised of, or is substantially comprised of “youngsands.” In the context of this invention a “young sand” means recent,Pliocene, and Miocene-age sediments (e.g., 0-5 million years of age).For such sands that are buried about 10,000 feet below surface level orless in a tectonically quiet area (an area with relatively fewearthquakes), RFIs will typically not be present or will besubstantially lacking, as described elsewhere herein.

In yet another aspect, the sample and material comprise a “tightcarbonate” material. A “tight carbonate” in the context of the inventivemethods means a material that comprises a substantial carbonate portion(e.g., at least about 90% of the material is comprised of one or morecarbonates), which exhibit low permeability (e.g., about 15 millidarciesor less, about 10 millidarcies or less, or about 5 millidarcies orless). In one aspect, the material is a material that is not suitablefor traditional S_(W) analysis, because electricity cannot sufficientlyflow through the material to give proper signals required fortraditional resistivity-based S_(W) analysis. The methods of theinvention also or alternatively can be applied to similar types ofmaterials from other settings that have similar types of resistivity,permeability, and/or conductivity issues.

The material typically is obtained in an analyzable sample or presentedin an analyzable sample. In a general sense, an analyzable sample can beany sample that has the necessary characteristics that allow it to beanalyzed using the specific conditions of the inventive method to bepracticed with the material. Skilled persons practicing this inventionwill be able to select such materials based on the other conditions ofthe method, the teachings provided here, especially in view of routineexperimentation and other known principles. For example, the size of thesample must be of sufficient size to provide enough material to beanalyzed. Additionally, the sample typically is handled in a way so asto preserve material in the sample to allow volatile substances to bereleased therefrom upon application of the force(s) to be applied inperforming the method of the invention. Other conditions and features ofcollection, storage, and/or handling of the sample may be selected so asto maintain the structural and/or chemical stability of the sample andvolatile compounds contained therein. The sample also typically shouldbe sufficiently free of materials that might interfere with theanalysis. For example, the sample typically is collected and maintainedin a manner such that it is substantially free of material from othersources that might “contaminate” the sample by causing it to providefalse information about the location it is taken from and its contents.

In still another aspect of the invention, the sample is obtained from aprocess that comprises the use of an oil-based mud. In general, drillingmuds may be water-based or oil-based. Oil-based muds often can createdifficulties for analytical methods such as fluid inclusion analysismethods known in the prior art. Those methods typically requireapplication of high heat and/or vacuum, such as, e.g., in a vacuum oven,applied over a long period in order to deal with samples obtained withoil-based mud drilling processes or risk interference from the oil baseof the mud and/or the oil material used for washing the samples. Suchproblems also exist with respect to non-fluid inclusion analysismethods, such as my other prior inventions. Methods in which hightemperature and/or vacuum is/are applied to remove oil-based muds cansuffer from the problem of also removing any endogenous hydrocarbons,organic acids, and/or oil. The ability to analyze such samples with themethods of the invention is yet another advantageous aspect of theinventive methods described herein. Samples also or alternatively can beobtained from water-based mud drilling operations, and in some instances(as exemplified herein) samples can be obtained for a site that wassubject to both oil-based mud drilling and water-based mud drilling.

As discussed elsewhere herein, samples may be sealed at or soonfollowing collection. In such aspects, about 0.5% to about 5% of thevolume of the sample may be made up of the target substance ortarget-related substance. For example, about 0.75%-about 3.5%, such asabout 0.8% to about 3%, about 0.9% to about 2.75%, or about 1% to about2.5% of the volume of the sample may be made up of the targetsubstance(s) (e.g., C5-C10 petroleum hydrocarbons) and/or targetsubstance-related materials. These amounts of target-related substancesare typically higher than the amount than would be found in materialsonly having such target substances or target substance-related materialsin fluid inclusions.

The amount of material collected or provided may be in excess of theamount that can be the subject of analysis at any time so as to provideassurance that there will be enough of the sample material to performrepeated runs of the method, etc. Any suitable amount of material can beused. A typical sample may be on the order of about 100 mg, but may beas low as about 1 mg, about 10 mg, about 25 mg, about 50 mg, or about 75mg. The maximum size of the sample often is determined by either thesample container size and/or the capacity of the mass spectrometryanalytical component of the device used in the method, if present.However, under the right conditions and using the right type of devicesamples as large as 1 g, 5 g, 10 g or even larger may be suitable foranalysis.

Typically, the sample will be collected from a material having arelatively known location. The location usually will include approximatedepth information in addition to longitude and latitude coordinates.Often the location may be a site of interest in petroleum or mineralexploration, such as an expected or known oil well, an oil well that hasbeen previously deemed non-productive, or a mineral mine, such as a goldmine.

In another aspect of the invention the sample is a fragment of a coresample. Core samples are commonly generated in oil exploration andrelated processes and are well understood in the art. Analysis of coresamples is considered important because of the preservation of oil orother target substances in the material. However, the process ofanalyzing core samples is often very time intensive. Advantageously,methods of the invention can be used to, e.g., to analyze fragments ofcore samples much more rapidly by, for example, evaluating thehydrocarbon content of such core sample fragments.

In most aspects of the invention, the sample is collected, stored, andprovided in a container. Such a “sample container” can be any suitabletype of container for maintaining samples in the context of the methodto be performed. In some aspects of the invention the sample is eitherdirectly analyzed from the sample container or is placed into adifferent analysis container prior to analysis. Sample containers caninclude or possess certain features that are advantageous in theperformance of some of the techniques described herein. Typically, thesample container is enclosed and usually at least partially isolatedfrom the environment (and preferably substantially if not completely oressentially completely isolated from the environment), so as to maintainsome portion of the volatile compounds in the sample over time, allowingfor the other steps of the method to be performed a period of time aftercollection (and storage). In specific aspects, the sample container iscapable of preserving a majority of the volatile substances in thesample at the time of insertion into the sample container (and in somecases more than a majority such as about 65% or more, about 70% or more,about 75% or more, about 80% or more, about 85% or more, about 90% ormore, about 95% or more, or even about 99% or more (e.g., 99.5%, 99.9%,or more) of the original volatiles are maintained) for a desired periodof time (which may be, e.g., 1 week, 2 weeks, one month, three months,six months, or even a year or longer). The maintenance of volatiles insuch instances can be under typical, limited, or special conditions(e.g., refrigeration or freezing may be required or desirable in somecases, but in many cases samples can be maintained under a wide varietyof temperature conditions without much additional care). In otheraspects, the sample container need only be able to maintain a sufficientlevel of volatiles to be able to be tested in the method, which may beless than 50% of the volatiles in the sample when the sample was loadedinto the sample container. In some cases, the amount of volatiles ismore than about 65%, such as about 75% or more, about 80% or more, about85% or more, about 90% or more, about 95% or more, about 97.5% or more,about 99% or more, or even about 99.5% or more (such as about 99.9% ormore) of the volatiles present in the sample when placed in the samplecontainer are maintained. In some aspects samples may be maintained inthe container with one or more substances that reduce the likelihood ofbiological activity that might reduce the probative value of the sample.

In one aspect, the sample container comprises a feature such as a seal,wall, cap, or the like (hereinafter simply referred to as a “seal”,unless context requires otherwise or unless otherwise explicitlystated), which is selectively penetrable by a flow channel device, suchas a needle, such that volatile substances in the container can bereleased when the sample container is penetrated without significantloss of such volatiles. Thus, the seal is typically of a material andconstruction such that it will not release volatiles upon puncture orother formation of passage through it to provide means for releasing thevolatiles to the other components of the system used to perform themethod. Methods for determining the integrity of the seal can be usedoptionally in the method, as described below with respect to collapsibleportions of the container. Loss from or contamination into the containerfrom the puncture or other type of opening of or passage through theseal will typically be non-detectable or will be of very small amounts(e.g., less than about 1%, less than about 0.25%, less than about 0.1%,or even lower amounts).

In another aspect, the methods, systems, and devices can be practicedwith containers that comprise a puncture-free method/step and/orpuncture-less component/system or device for providing access to sealedvolatile substances inside a sealed sample container. For example, inone facet the invention provides a system and method in which a samplecontainer, such as a sample tube, is able to be selectively open to thesystem, such as facets wherein the sample containers are sample tubeswithin an enclosed autosampler and the remaining portion of the systemcomes into fluid communication with the container/sample uponpositioning of the sample tube into a position in which the open end ofthe sample tube/container is allowed to interface with an entryway tothe remainder of the device/system, typically, for example by means ofan automates vacuum sealing connector, which may, e.g., cause an O-ringto be tightened between the system and the open sample tube, thussealing the tube to the system without any puncturing or any needlepassageway. In this kind of facet, the system/device does not permitsignificant loss of contents from the sample tube in the system, asdescribed elsewhere herein with respect to other sample containers(e.g., less than about 5%, less than about 3%, less than about 1%, lessthan about 0.5%, or even less than about 0.2% of the contents are lostafter placement into the sample container, in this case in thesystem/device).

In another aspect, the sample container also or alternatively comprisessufficient space beyond that which is occupied by the sample itself,such that some portion of the container can be filled with releasedvolatiles. Accessible space also often is provided for the needle orother channel forming member or device to allow access into the samplecontainer, in aspects where a sealed container is provided. Thus, abouttypically about 2-20%, such as about 3-15%, e.g., about 4-10% of thecontainer, when sealed, is left as open space providing space for gasand also for flow channel device entry. The container may have more openspace before sealing to also provide room for the seal (e.g., about5-25% of the container may be designed to be open before the sealing).

In still another aspect, the sample container also or alternativelycomprises a portion that is designed to be modifiable under certainconditions, such as being collapsible under mechanical pressure, suchthat the force of any sufficient mechanical pressure applied to thesample container can be transferred to the sample and thereby cause orincrease the release of volatile substances, preferably withoutdisrupting the structural integrity of the sample container in anymanner that would cause release of any amount or any significant amountof volatiles that are released in the container (e.g., less than about1%, less than about 0.25%, less than about 0.1%, or less than anydetectable amount of volatiles are released from the application offorce on the collapsible portion of the sample container) and/or causingthe contamination of the container space (and volatiles containedtherein) with substances from the surrounding atmospheric environment(such as air in the laboratory). The method can comprise monitoringpressure in the container or pressure in the container as connected tothe analytical device, as one measure to make sure that no loss and/orcontamination is occurring due to leaks. Other methods also oralternatively could be performed to ensure that such leaks of thecontainer are not occurring, such as analyzing compounds in theenvironment around the container using conventional methods. As notedabove, such techniques also can be applied to ensuring the integrity ofother aspects of the sample container or other elements of the systemthat are used in the practice of the methods.

In typical and preferred aspects, the sample container is specificallyadapted for use in one of the inventive devices described elsewhereherein for performing the various methods of the invention. Featuresthat the sample container typically will comprise in order to besuitable for use in such devices include (1) a penetrable seal which iscomprised of a seal material that is both (a) inert with respect to and(b) is at least substantially if not entirely impervious to the samplematerial and volatile materials contained therein (by “inert” it ismeant that the material will not chemically react with the volatilematerials and the sample materials, and does not give off volatilesunder the conditions in which the method is performed, therebymodulating the analysis), and (c) is adapted in shape and size to sealthe body of the container with respect to transmission of gasses andother materials that might partially or entirely interfere with,corrupt, or diminish the effectiveness of the analysis, and, preferably,and (2) a body comprised of a material that can be subjected to forcesto be used in the method for drawing out of volatile materials, which inpreferred aspects includes crushing of the sample container (andmaterials within the container) (e.g., the sample container bodycomprises or is composed of a material that is crushable under the forceused by the device, allowing the sample of the material to also becrushed while releasing volatile materials from the sample into thecontainer, the sample container being constructed in such a manner andof such materials so as to not be compromised, and so as to not lose itssealing properties on being crushed as discussed elsewhere). Theprinciple of inert material discussed in this paragraph also typicallyapplies to all elements of the sample container and other elements ofthe system used in the practice of the method. Thus, for example,tubing, trapping devices, and analytical devices incorporated into thesystem will similarly be selected based on being inert with respect tothe sample and volatiles expected to be present and subjected toanalysis.

In certain aspects, the method comprises multiple rounds of crushing,such as crushing the sample container by application of crushing and/orsqueezing or compression forces, typically from different directions. Instill a further step, the method comprises restoring the container, atleast partially, to its original shape after application of a crushingstep or multiple crushing steps. The step of crushing or compressingsamples can be performed at any suitable time. In one aspect, the stepof crushing is performed after the application of other forces thatpromote the release of one or more volatile substances from the sample.In another aspect, the step of crushing or compressing the sample isperformed prior to the application of other forces on the sample topromote the release of volatiles, such as the application of pressure tothe sample. In still other aspects, as described elsewhere herein, thestep of compressing the sample can be performed independently ofextracting or releasing volatile compounds (and vice versa).

The preferred sample container is at least partially or relativelyflexible in design to allow for capturing a variety of sample typesunder a variety of conditions. Methods of the invention can varyconsiderably in terms of pressure, temperature, gas content, and otherrelevant factors. The sample container and other elements of the systemtypically are selected to be able to operate under a wide variety ofsuch conditions. Pressure conditions are provided elsewhere herein thatcan help characterize such suitability. Temperatures used in practicingmethods of the invention can also vary considerably, especially wherehigh temperatures are used to remove material and freezing is used as atrapping method. In this respect, the overall system, including thesample container, may see temperature ranges from about −273/−270degrees C. (“degrees C.” herein means degrees Centigrade) to about 500degrees C., such as about −195 degrees C. to about 200 degrees C. Inmany aspects, the temperature in the system will not exceed or evenpossibly not reach 100 degrees C. In other aspects, the temperature inthe system will not exceed or possibly not reach 50 degrees C.,particularly in the sample container. By remaining at such temperaturesmore affordable materials can be used in the practice of the method.Also, these extreme temperatures may not be reached in all parts of thedevice. For example, heat may be applied to the sample container, butfreezing temperatures may only be applied to the trap device.

The flow channel or needle is used to penetrate or otherwise form apassage for the flow of gasses from the sample container (or moreparticularly in typical embodiments a needle is used to penetrate a sealcomponent of or associated with the sample container). In embodimentscomprising the use of a needle, the size of the needle typically isselected such that it provides sufficient flow of volatiles from thesample container to the rest of the system but is not so large as tocause puncturing of the seal and release of seal material (or otherportion of the container) into the interior of the sample container. Aneedle used in the methods herein can have any suitable configuration ofinlets (holes) to receive the gas. A single hole, placed in the side, ortwo holes, placed on each side, of the needle, is typical. Sideplacement of the needle can help ensure that the needle inlet does notbecome clogged after passage through a seal or sidewall of thecontainer. A type 5 needle (by Hamilton), for example, provides such abalance with respect to exemplary devices described herein.

As noted above, sealed samples can be stored for significant periods oftime and still be successfully analyzed using the methods of theinvention. Some volatiles can be trapped in hermetically sealed voids insolids, such as fluid inclusions in rocks. In some embodiments, suchvolatiles can be analyzed years or decades after the sample iscollected. The volatiles hermetically sealed in the solid can bereleased by crushing the solid, or by thermally heating the solid untilthe volatile filled voids decrepitate.

Other volatiles can readily escape from their solid, liquid or gaseoushost. Such volatiles include oil, water, and gas in pores in drillcuttings or core, or within the drilling mud used by the well. It willtypically be desirable that such solid and liquid samples are sealed asquickly as practically possible to permit the most representativeanalyses of the oil, water, and gas in the Earth's interior. Asdemonstrated and discussed elsewhere herein, the methods of theinvention can be practiced with old, exposed materials, in which some oreven significant loss has occurred, but better results are oftenobtained with samples that are sealed within a short period of time fromthe sample reaching the surface or being exposed to changed atmosphericconditions that would allow for release of relevant substances.

In one aspect the inventive methods are practiced without application ofa significant vacuum or pressure on the sample prior to performance ofthe method. My prior inventions and other prior art methods often willapply significant vacuum or pressure and/or significant temperature tosamples prior to analysis of the materials. The lack of such a step incertain aspects of this invention is yet another way in which suchaspects are significantly distinguishable from the prior art.

While sample containers that can be crushable or otherwise compressibleare often preferred, a large variety of sample containers may beadequate for samples that do not require mechanical disruption (e.g.,glass vials, graphite tubes, or other containers that are impermeableand inert) in the practice of certain aspects of the inventive methods.Thus, for example, if there is to be no mechanical disruption eitherglass vials or sealed metal tubes can be used as sample containers.Various hoses made of rubber or other polymers might also oralternatively suffice if they can be hermetically sealed. Even Mylar orplastic bags may suffice for some applications. In some aspects of theinvention containers also can be comprise or primarily, nearly entirely,or entirely be made from carbon fibers. Indeed, any container that canbe hermetically sealed might be sufficient, depending on the nature ofthe bulk material being captured.

Commonly, the sample container comprises a septum or a cap (e.g., asynthetic rubber or nitrile cap) that is inert and through which asuitable flow channel device such as a needle can be readily passedwhile maintaining the seal's integrity. In such aspects, the volatilespurged from the sample will enter the inlet lines through the needle.Such elements of the sample container are optional. In another exemplaryembodiment, the sample container is sealed using a compression fittingthat can be automatically applied, with subsequent rupture of the samplecontainer to release the volatiles into the system's inlet. Anotherapproach that may be more appropriate in some instances would be toinsert the entire sample container into a hermetically sealed chamberthat is attached to the inlet system, followed by subsequent rupture ofthe sample container to release the volatiles. The sealed samplecontainer could be introduced automatically one at a time through anappropriate port, or an individual sample or multiple samples could bepreloaded and sealed into part of the inlet system.

If the sample is to be crushed and is on the exterior of the inletsystem connected by a needle through a septum, cap, or some other means,such as a remotely controlled compression fitting, it can be desirablethat the container can be crushed without leaking, and that any motionof the sample during crushing does not break the seal between the samplecontainer and the inlet system. The selection of parameters for samplecontainers, seals, other elements of device, and compression/crushingmethods in general will be selected such that a seal is maintained andthere is no undesirable loss of volatiles or material or contaminationthereof. A brass cylinder sealed on the bottom with a neoprene plug andsealed on the top with a nitrile cap, for example, can be a suitablesample container. However, other metals and other sealing methods may beemployed in the sample container or systems/methods of the invention.For instance, a brass rod could be partly drilled out to make a vesselsealed on the bottom, thereby eliminating the need for the neopreneplug. Similarly, the cap could be made of a variety of compounds,however Nitrile has very good sealing properties for hydrocarbons andmost other volatiles.

It is typically important that if a cap is used to seal the samplecontainer that it can be hermetically sealed to the body of the samplecontainer. This can sometimes be achieved by simply having the cap'sresting diameter be sufficiently smaller than the tubes diameter so thatthe cap needs to be stretched over the tube or fit into the tube thatforms the body of the sample container. Stretching in this manner mightby itself typically result in a sufficient seal. If not, then additionalmethods must be employed to affect a hermetic seal between the cap andthe tube, such as applying a compression device such as a hose clamp orzip tie or a metal ring having a diameter greater than the tube but lessthan the diameter of the cap when covering the tube, around the outsideof the cap. Other methods of sealing the cap to the tube can includeapplying glue, or epoxy, or wax, or grease, or some other sealingsubstance between the cap and the tube. It is also possible instead of acap to use a septum crimped to the top or some other part of the samplecontainer for a needle to pass through, or even a polymer plug, such asa neoprene plug used to seal the bottom of sample containers. For asample container that is secured to the inlet system by an outercompression fitting, or some other means such as a screw fitting as on ahose (or a threaded cap), that is a larger than a needle can form achannel or flow path between the sample container and the inlet system.Such a sample container adapted to be in direct material communicationwith a wider diameter inlet system can be sealed using a wide variety ofsealing material including metals, polymers, glass, even such exoticmeans as a salt or sugar plug, glue, or other adhesive or sealingmaterial. The sealing material typically will make a hermetic seal afterthe sample is captured up to the time it is ruptured, and must beamenable to rupture after attachment to the inlet system. Similarly,sample containers that are loaded entirely into the inlet systemgenerally will be hermetically sealed following loading of the sample,and usually will maintain that hermetic seal until somehow ruptured ormade permeable to the substance(s) of interest at the appropriate timeinside the inlet system.

As exemplified by the foregoing passages, it can in some aspects beadvantageous and/or important that the overall system (sample container,inlet, or other elements of the system) are configured and constructedsuch that the overall system maintains its integrity, particularly withrespect to the sample and volatiles released therefrom, upon theapplication of any forces applied in the method, such as any crushingforce. An example of such an approach is the use of a needle-associatedslug, as exemplified elsewhere herein. In aspects where application of acrushing force causes parts of the sample container to move, becomedeformed, or otherwise become displaced, such movement may permit thehole that the needle passed through to become enlarged, which might, ifnot addressed, allow undesirable release of materials from and/orcontamination of the system/sample container. A slug associated with theneedle, such as by use of a compression spring placed around the needle,forcing intimate contact between the slug and the cap or seal, canassure the user that any such expanded hole formed in the cap or sealwill still not permit such release or contamination. However, otherapproaches can similarly be used to ensure that the entire samplecontainer/device system maintains the integrity of the material,depending on the configuration of the device and sample container (andsteps of the method) and any released volatiles and the invention is notlimited to this slug/spring approach. For example, if high temperatureis applied to the sample container, the sample container and inlet maybe configured and composed such that the application of such hightemperature does not allow the formation of any cracks or openings thatwould similarly allow for undesirable contamination or release.

In one aspect, the crushing of a sample container and sample containedtherein is used to assess the ductility (and/or porosity) of the sampleand, correspondingly, the material. In a method in which a material ofrelative standard strength (in terms of crushability under a relativelyfixed amount of crushing force) (such as by using the same quality ofmaterial in the same thickness, etc., within very small variations(e.g., about 10% variation or less, such as about 5% variation or less,such as about 1% variation or less in thickness and other relevantcharacteristics), is employed with a standard measure of sample (again,given the ability to have similar variability in the amount), the amountof collapse of the container, reflecting also the crushability of thesample, can be correlated to either the strength of the material and/orthe ductility of the material (and/or porosity of the material). Suchmethods can be advantageous where the method is performed in connectionwith oil fracking or similar methods in which ductility of the materialis a very important feature of the material.

Mapping the ductility of samples versus measured drilling depth invertical well, or in a horizontal well, can provide information as towhich sections of rock are most likely to have low risk of frackingfailure. Fracking failure occurs when the rocks that have beenhydraulically fracked do not have sufficient mechanical strength tomaintain the induced fractures open following the injection of aproppant, usually sand. This aspect of this invention therefore istermed “frackability”, as an advantage of this aspect of the inventionis permitting practitioners of the method to map those sections of rockdrilled by a petroleum well that will maintain open fractures followingfracking and proppant injection. This can be especially critical nearestto the borehole, since if the fractures near the borehole do not remainopen, no or only a very diminished amount of oil and/or gas can beproduced.

One realization of this aspect of the invention is to measure acontainer, such as a sample tube as described herein loaded withcuttings, after squeezing with a known force, with a micrometer or otherappropriate measuring device. Such a method can be performed manuallyafter the sample has been squeezed, or can be done automatically as partof the analytical process using a device such as a linear translatorthat mechanically monitors how far the pneumatic pistons are extendedafter squeezing the sample is completed, or a device such as a laserranging instrument, also to measure the total extension of the airpiston, or other squeezing means, after the sample is totally squeezedto its final thickness.

Real time measurement of the squeezing process by an appropriatemeasurement means allows additional information to be collected thatprovides useful and necessary information for the design of a optimallysuccessful fracking job. This includes measuring how the air piston orother squeezing means deforms the sample as a function of time and/orthe amount of pressure applied. The sample deformation may be relativelyrapid, or relatively slow. The deformation may be a smooth continuousprocess, or may be a series of discontinuous forward lurches. Also ofinterest is how far the piston is pushed back by the sample after thepressure is released from the air piston, that is how much does thesample recover. The collection of these data during the squeezingprocess will allow for the calculation of various parameters vital to asuccessful fracking job, including Poisson's Ratio and Young's modulus.

Analyses of these parameters using the current state of art in theindustry usually requires the expensive acquisition of a conventionalcore, or rotary sidewall cores, followed by expensive and time-consumingmeasurements at a laboratory usually some significant distance from thewell. Often it is months after the well is drilled before the results ofthese other measurements are known.

Frackability from petroleum drilling cuttings can be rapidly determinedeither in the lab or on the well site. Turnaround time for transport ofsamples to the lab followed by analyses can be less than 24 hours. Thisis fast enough for the data to be used in deciding the final manner inwhich the well will be completed, such as what zones will be perforated,or where a horizontal lateral will be landed following the drilling of avertical pilot hole.

Even more timely results can be had by measuring frackability of thewell site while the well is drilling. This can be done by manuallycollecting samples and then loading in an instrument at the well sitefor analyses. In another aspect of the invention, frackability can bedetermined at the well site using an automatized instrument thatcollects a sample of drill cuttings and squeezes them and monitors thedeformation. Such an automated apparatus would not require loading thecuttings samples into a container. The cuttings can fill a collapsiblecompartment in the well site frackability apparatus. Following fillingof said compartment with cuttings the squeezing mechanism of theapparatus squeezes the cuttings while the amount and systematic of thedeformation of the sample is recorded using a linear translation orother type of measuring meter. The data thus collected would then bestored on a computer, and can be instantly integrated with otherdrilling parameters generated by other instruments on the well,including logging while drilling tools, such as gamma ray logging whiledrilling, rate of penetration, weight on bit, mud log shows, etc.

Real time frackability data can be combined with other real-time data todetermine the optimum way to drill the well. The data can be used tohelp steer lateral horizontal wells to stay in the optimum formation.

In one aspect, the invention provides a method for analyzing thefrackability (ductility or hardness) of a material, such as a geologicformation, which comprises the steps of (a) providing one or moreanalyzable samples of the material, (b) subjecting the sample to one ormore forces that are capable of compressing material of a given hardnessor ductility, and (c) determining the amount of compression of thesample caused by the one or more forces. The analyzable sampletypically, but not necessarily, will be from or associated with apetroleum well or petroleum exploration. The most basic form of thefrackability method is distinct from prior approaches used to assesshardness of a geologic material, which either depend on scratching(e.g., the classic Mohs scale testing) or penetration of a point of thematerial or point contact with a surface of the material (such as byusing the Schmidt rebound hammer), although such methods can be combinedwith the basic frackability method. In one aspect, the compression forceis applied to at least an entire side of the sample. More typically, thecompression force will be applied to multiple sides of the samplecontemporaneously (within 2 minutes, within 1 minute, within 10 seconds,within 5 seconds, within 3 seconds, or within 1 second of each other),and, most often, simultaneously. Frequently, the compression force(s)will be applied isotopically, that is to say that it/they will beapplied to all sides of the sample contemporaneously or simultaneously.Where advantageously combined with other methods of the invention, thecompression study will be conducted in a compressible container, asexemplified elsewhere herein. The sample often is either a cutting ortaken from a core sample associated with a petroleum well or petroleumexploration. Thus, in many aspects the size of the sample will be thesize of a cutting, as explained elsewhere herein. In one aspect, themethod is performed on cuttings that are associated withpetroleum-associated mud. In other aspects, the method comprises washingthe sample prior to crushing.

A further distinction in the typical application of the frackabilitymethod and methods of assessing hardness of geologic materials in theprior art is that the frackability method, especially when applied tocuttings, is applied to a large number of materials (at least 10,typically at least 20, and often more, such as at least 25, at least 30,at least 40, at least 50, or more) that are obtained from differentdepths and/or different locations within a relative zone of depth, andfrequently such materials are brought to the surface within therelatively short amount of time that is required for petroleum drilling(e.g., about 1 day to about 12 months, such as about 1-300 days, about1-250 days, about 1-240 days, about 1-200 days, about 1-180 days), suchthat the samples comprise a number of samples obtained during thisperiod (e.g., a majority of the samples are obtained within 200 days ofeach other or at least 20, at least 30, at least 35, at least 40, atleast 50, or more, of the samples in the analysis are obtained within atleast 240, at least 180, at least 120, at least 90, or at least 60 daysof each other). Currently, assessments for fracking suitability havetypically made using either (1) minerology assessments, which determinethe mineral structures present in the drilling area or potentialdrilling area through sampling, (2) x-ray diffraction methods tosimilarly assess the geologic content of the area (within the detectionlimits of that method), and (3) assessing the total organic content ofthe exposed area of the material. These practices can be combined withthe compression frackability methods provided by this invention, incertain aspects, to provide additional information about the material.However, in another aspect, compression frackability can be performed asan assessment method without employing any of these methods.

A collection of samples evaluated in the frackability, such as cuttings,can consist entirely of samples obtained from locations in the materialthat are at least about 0.5 feet apart, and typically (but notnecessarily) up to about 100 feet apart from one another (e.g., they canbe from depths of a well that are at least 0.5 feet apart, at least 0.75feet apart, at least 1 foot apart, or even further apart, such as atleast 18 inches apart or at least 24 inches apart), or the set ofsamples can substantially consist of (e.g., at least 85%, at least 90%,at least 95%, at least 97%, or at least 99%) samples obtained fromlocations characterized by such differences, or the set of samples canbe characterized in that a majority of the samples were obtained fromlocations having such differences in space, or at least a largeproportion (such as at least about 10%, at least about 20%, at leastabout 25%, at least about 33%) of the samples were obtained fromlocations that have such relative spatial separation. In view of thepossibility of lateral drilling the separation between the samples alsoor alternatively could be in the same relative zone of depth (e.g.,within the same 500 ft, 400 ft, 350 ft, 300 ft, 250 ft, 200 ft, 150 ft,100 ft, 50 ft, 30 ft, or 25 ft vertical zone). In some aspects, multiplesamples from approximately the same location are tested, but the setcomprises a number of samples from different locations (e.g., at least10, at least 20, at least 30, at least 50, at least 100, at least 150,at least 200, at least 250, at least 300, at least 400, at least 500, atleast 750, at least 1,000, or more samples, from locations in thematerial that are at least about 0.75 ft separated from each other). Thenumber of total samples used in such a method will typically be greaterthan about 10, such as greater than about 20, and often can besignificantly more samples, such as at least 50, at least 100, and canrange from 10-5,000, 10-3,000, 10-2,500, 15-3,000, 15-2,500, 20-3,000,20-2,500, 25-3,000, 25-2,5000, 25-2,000, 20-2,000, 10-2,000, 20-1,500,25-1,500, or 10-1,500 samples, The total area of assessment can besignificant, such as at least about 0.25 miles, 0.33 miles, 0.5 miles,0.75 miles, 1 mile, 1.25 miles, 1.5 miles, 1.75 miles, 2 miles, or more,in depth and/or in horizontal area, reflecting lengths of modernpetroleum wells. Thus, the frackability methods of the invention canprovide a relatively fast map of the suitability of fracking a wellsite. In some respects, the entire analysis is conducted near the wellsite (such as within 200 feet of the well site). This can be achieved byusing devices of the invention that compress material near the point ofseparation of cuttings and muds, for example, in petroleum drilling.

In some aspects, the compression frackability methods of the inventionare combined with the other methods described herein for assessinghydrocarbon content of a material through release of volatile compounds,such as organic acids, which may be released using the methods describedherein (e.g., application of gentle vacuum, trapping, and optionallyanalysis by sensitive methods such as mass spectrometry analysis). Inother aspects, the frackability methods of the invention and thevolatile compound analysis methods of the invention are practicedseparately. Similarly, for the devices of this invention, such devicescan comprise combined frackability and volatile compound analysiscomponents/systems, but the invention also provides devices thatcomprise these functions as individual features.

Some aspects of the invention, particularly those in which releasedvolatile compound analysis will be performed as a part of the inventivemethod, are characterized by comprising a step in which sample materialis stored quickly, and typically in a sealed manner, after arriving atthe surface or otherwise being exposed to normal atmospheric conditions.For example, at an oil well site such a method can comprise collectingcuttings in a sealed container within a short amount of time after suchcuttings reach the surface. The time for collection can vary with thenature of the sample, the method to be applied, and the targetmaterial(s) that are sought to be identified by the method. In anexemplary aspect of the invention, the samples are sealed in a sealablecontainer in about 5 minutes or less, but more typically the time willbe about 3 minutes or less, about 2.5 minutes or less, about 2 minutesor less, or even about 1.5 minutes or less, such as about 1 minute orless. Samples can be subject to washing immediately before sealing in asealable sample container. Sample washing can be carried out by anysuitable method. More generally, but not necessarily, cuttings or othermaterials typically are stored such that volatile compounds containedtherein are not lost below limits detectable by the method. Volatilegasses and chemicals that rapidly expand under atmospheric pressure andnon-constrained conditions, such as petroleum-related hydrocarbons, canbe readily released from such materials once they reach the surface.Accordingly, it is advantageous to store materials to be analyzed suchas cuttings within one or more containers that will ensure no release orlittle release of such substances during the time the material is to bestored and/or transported. In a preferred aspect, the materials arestored in one of the devices described elsewhere herein, and mostpreferably such a device is configured to fit securely within one of theanalytical devices of the invention described further elsewhere herein,such as by mating with an inlet or by using a flow channel device, suchas one of the needle devices discussed herein.

A filter material also can be added to the sample container. Any type ofsuitable filter material can be used. Suitability in this respectgenerally means that substantially all (e.g., at least about 95%, suchas at least about 99%, or at least about 99.9%) of the material(excluding the volatiles released from the material) is maintained inthe interior of the sample container and does not enter or come intocontact with the flow channel or inlet. Simple filter materials such ascloth materials and cotton pellets have been demonstrated to be suitablefor this purpose. These materials, as with other materials used in thesample container and throughout the system must be inert with respect toreacting with volatile chemicals and emitting materials that wouldinterfere with the analytical aspects of the inventive methods.

In one aspect of the invention, the sample(s) that is/are analyzed inthe method is or comprises a drilling mud. Muds have been discussedelsewhere herein. The mud can be an oil-based mud or a water-based mud.The analysis of muds typically means that more than one mud samples aretaken. This is because material can be maintained in a mud over severalre-uses of the mud (or passages of the mud to the drill bit point andthe surface where a sample might be taken). Accordingly, samples may betaken at points that correspond with an “up mud” (mud arriving at thesurface) and a “down mud” mud going back into the well, which will helpto identify changes in the mud over time, aiding in the analysis of thematerial through studying the mud. In one aspect, the method comprisesthe analysis of mud materials and cuttings. In still another aspect themethod comprises the analysis of mud materials, cuttings, and/orfragments of core samples, such as samples of each of these categoriestaken from a petroleum well or petroleum exploration site.

The material and sample are typically a solid (as in the case of acutting), but in other aspects of the invention the sample and/ormaterial is a liquid or a gas, and in still other aspects the sampleand/or material is a mix of two or more of a solid, liquid, or a gas, ora combination of all three forms of material. For example, in anindustrial setting, samples can be taken of the air to ensure that theamount(s) of certain compounds (e.g., benzene) are within certainlevels. In still another embodiment the method is applied to look forseeping, such as gasses seeping into and/or out of a geologicalformation. Geothermal activity also can be assessed by the method. Inanother aspect, the method can be practiced with a liquid, such aswater, to assess the level of certain substances in the liquid (such ascontaminants in water samples). As noted elsewhere the material can beof natural, synthetic, or semi-synthetic origin, and may be generatedfrom a variety of origins and/or settings, such as industrial solids,soft materials, liquids, and air, or other gases.

In preferred aspects, the method is applied to analyze the volatilecompound content of the material. Volatiles in rocks typically containimportant information used for petroleum, geothermal energy, and mineralexploration and production. Volatiles in rocks can also be used todetermine the suitability of quarried stone for road and buildingconstruction. Volatiles in rocks and soils may also provide informationbeneficial to ecological and environmental studies. Volatiles in solidsthat form as a byproduct of various industrial or civil processes, suchas scales that can form in the casing of oil, gas, and water wells, canprovide information that may help design processes to inhibit theformation of such unwanted solids. Volatiles in man-made solids such asbricks, concrete, ceramics, glass, and plastics can be used to ascertainproblems in their manufacturing process, or to evaluate their utilityfor various applications. Volatiles that occur in solids that form innatural biological systems, such as bone, teeth, kidney stones, fingerand toe nails, may provide insights that could help to maintain orimprove the health of the individual or community from which thesesolids originated. Volatiles in softer tissues from plants and animals,including humans, may also offer diagnostic information that may beuseful to the health of the source organism. Such methods may haveapplication in testing in food safety testing, food viability, foodstorage, and/or shelf-life, or the like. Volatiles in industrial andnatural liquids also contain a wealth of information that can impact thesuccess and profitability of petroleum, geothermal energy, and mineralsexploration and production; the efficiency and profitability. ofmanufacturing and other industrial processes; and the health andwell-being of the environment, organisms and communities. Variousexplosive products may also have distinct volatile signatures that couldbe detected with the device described herein, thus volatile monitoringof air or solids may have benefits in keeping people, communities, themilitary, and law enforcement secure.

In one aspect of the invention the sample is taken from an outcrop andthe material comprises an outcrop. Outcrops are geologically importantformations. In one aspect, outcrops (outcroppings) are used as acomparator to subterranean materials, such as materials obtained from amine or drilling site. Such materials may also contain evidence ofmaterials seeping to the surface.

The material typically is dry, but in some aspects of the invention ismoist or even wet (e.g., in the case of a liquid or a mud). In someaspects of the invention it can be important to ensure that the amountof a liquid, such as water, in the material, is not too high so as toovercome the capacity of the mass spectrometry device. However, ingeneral, this is not a limiting factor, and the skilled artisan will beable to assess if any such situation arises.

As already noted herein, the material, and thus the sample, willtypically contain one or more volatile substances that will eitherpassively release or be released upon the application of one or moreforces on the sample. In either case, a gas will be released from thesample that contains one or more volatile substances, although, asdiscussed elsewhere herein, the sample can also contain non-volatilesubstances, which may also or alternatively be collected, andconsidered, as part of the analytical aspect of the inventive method.The nature of the volatile substances contained in the sample can varyconsiderably and the inventive methods can be practiced with varioustypes of volatile compounds. In specific aspects, however, the sampleand material contain a significant amount of one or more specific targetsubstances. For example, in the case of drill cuttings, taken frompetroleum production of exploration sites, the sample will containdetectable amounts of one or more species of C1-C20 hydrocarbons andrelated compounds that contain oxygen, nitrogen, sulfur or otherheteroatoms; organic acids (e.g., C1-05 organic acids, particularlyC1-C3 organic acids, and most commonly acetic acid, carbonic acid,and/or formic acid); and/or one or more inorganic gasses, such ashydrogen, helium, carbon dioxide, carbon monoxide, water, nitrogen,argon, oxygen, hydrogen sulfide, carbonyl sulfide, carbon disulfide,and/or sulfur dioxide. In one embodiment, the sample comprises C1-C15hydrocarbons, such as C1-C14 or C1-C12 hydrocarbons and the methodcomprises analyzing one or more of such hydrocarbons. In still anotheraspect, the sample comprises C1-10 hydrocarbons and the method comprisesanalyzing one or more of such hydrocarbons. In aspects that are oftenpreferred the invention also or alternatively is characterized by thedetection of acetic acid, carbonic acid, and/or formic acid contained inthe sample or formed from application of one or more forces on thesample in the practice of the inventive method. In this respect, thesample can be characterized as comprising one or more compounds thatform such compounds, or by having material that can form carbon dioxide,carbon monoxide, methane, and/or water.

In another facet, the inventive methods provided herein can becharacterized in that such method comprises conducting an analysis ofthe sample for one or more substances containing a carbon chain of fiveor more, such as six or more, or seven or more carbon atoms. In somecases, the method comprises heating the sample or gasses to assist withthe analysis of longer chain hydrocarbons or other carbonchain-comprising compounds, such as hydrocarbons having a backbone ofmore than 10 carbon atoms. For example, the method can comprise heatingthe sample or gas (or the device containing either or both) to about130° C. or more, about 140° C. or more, or about 150° C. or more, toassist with the analysis of such longer-chain hydrocarbons. In this andother respects, the method can comprise controlling the temperatureduring which some or all of the process is performed, such as thetemperature at which gasses are released and/or analyzed by theanalytical processes of the method. Such methods typically can compriseheating the entirety of the system from the inlet, through to the trap,to the mass spectrometer, and through to the exit. In other aspects, itis preferred that the method is generally performed at room temperature,although in such aspects it may also comprise using freezing as a meansfor trapping volatiles and/or applying heat to release compounds from afreezing trap mechanism or media.

In some aspects, the invention is characterized by not creating newvolatile compounds in the sample, such as forming volatiles fromhydrated minerals (where water is a part of the crystal structure, suchas silicate clay minerals; hydrated oxides, such as brucite (MgOH2) andgoethite (FeOOH); and other water-bearing mineral substances such ashydroxyl apatite; etc.) or where, e.g., carbon dioxide is part of thecrystal structure (such as calcite (CaCO₃), dolomite (CaMg(CO₃)₂), andsiderite (FeCO₃)); and solid and liquid hydrocarbons not volatile as agas under the analytical conditions in which the methods of theinvention are performed, such as C20 alkanes or various bitumins orkerogens; or any other substance that is normally not a gas or normallyemits a gas under such conditions.

In practicing methods of the invention one or more gasses is/aretypically released or extracted from the sample of the material. In somecontexts, the gas can be released passively (without application offorce or without application of a significant force); e.g., by exposingthe sample or the container comprising the sample to a release channelor release passage, such as a needle or similar device which penetratesthe container containing the sample. In other contexts, as notedelsewhere herein, the methods also or alternatively can compriseapplying energy to the sample, such as by mechanical force, e.g.,crushing of the sample or crushing of a container that has a crushableportion and that contains a crushable sample. In either case, the gas orgasses are released from the sample of material and then are allowed toflow such that one of the further steps of the method can be performedon such gas. The amount of time required for the gas to be release canvary with the conditions of the method, including the material, whetheror not forces are applied to the sample, the time in which gasses arepermitted to be released from the sample, and the sensitivity of theanalytical methods performed on the gasses. Using the guidance providedherein skilled artisans will be able to determine these conditions. Forsamples that are analyzed at atmospheric pressure without theapplication of force a time of about 1 second may be sufficient, forexample. Longer or shorter periods of time may be suitable, but such arelatively short period may be desirable. Longer periods may cause thesample to be under lower pressure conditions because of the relativelylower pressure condition of the device.

In many aspects of the invention volatile substances are extracted froma sample by subjecting the sample to various levels of vacuum. For somesamples, important additional information is obtained by subjecting thesample to a range of increasingly lower pressures, in other words toincreasingly higher levels of vacuum, and analyzing the chemistry ofeach individual aliquot extracted at each individual extractionpressure. This has proven to be especially useful for solids,particularly for various rock samples including outcrop, core, andcuttings samples as applied to the exploration for and production of oiland gas. Depending on the sample and the problem being addressed variousother processes may be applied to the sample prior to any vacuumextraction, in between vacuum extraction steps, or even during a vacuumextraction step, as will be discussed further herein. In one example,another process that can be applied, and which is described elsewhereherein, is crushing or squeezing the sample or applying any process thatmechanically disrupts the solid sample. Other processes that mightdisrupt the sample include sawing, or tumbling, or exposing tovibrational energy at any number of frequencies. Another process thatcould be employed is heating the sample; one effect of which can bedisruption of the sample by thermal decrepitation of fluid inclusionsand/or other structures in the sample. Chemical processes and/orapplication of energy also or alternatively may be applied to the samplein the performance of the method, such as, for example, applying an acidto the sample so as to dissolve certain substances. It is also possiblethat in some instances a combination of two or more of these or otherdisruptive processes may be usefully applied in the practice of theinventive methods.

The method also may include one or more steps performed before releaseof gasses, or between release of gasses (in methods in which there aremultiple release steps or multiple samples analyzed). In one aspect, themethod comprises purging some amount of air from the sample, e.g., byapplication of vacuum. In such embodiments the time the vacuum purge isapplied will generally be such that the amount(s) of volatiles that arepurged with the air is sufficiently small to justify the purging step.This may comprise, for example, only 1 or 2 second application of vacuumpressure, so as to lower the pressure from about 1000 millibars to about50 millibars (but these are only exemplary figures). However, such apurging step can be important where the presence of air as a contaminantwill interfere with the analysis. This may be important with respect toanalysis of older samples contained in open environments.

In a further specific aspect, the inventive methods can comprise purgingthe sample, which may be a sealed sample, and replacing the purged airwith another gas, such as argon, nitrogen, or helium, or any othersuitable gas as determined by the specific advantage gained for thespecific problem being addressed and the specific host solid andspecific volatiles being analyzed. argon is typically preferred asnitrogen and helium may be relevant in the analysis of the sample.

These steps of purging (and optionally replacing) air or othersurrounding gas provides a mean of removing potentially interferingsubstances in the air or other gas in which the sample is contained,which might provide false signals in the analysis (e.g., confusingmethane with oxygen or nitrogen species found in air). Other methods ofaccomplishing the same goal may be available in the art and likewisesuitable, but this method is preferred in many aspects of the invention.For example, in one alternative, the air or gas in an inner samplecontainer is displaced with a liquid, such as a diffusion pump oil, andthe inner sample container placed in a surrounding, outer container. Theinner sample container comprises or typically is entirely made of amaterial that can be crushed or compressed by application of a force. Avacuum is applied to remove any air from the surrounding container,creating a vacuum condition in the space formed by the surroundingcontainer, and the entire sample container sealed. A force thatcompresses or crushes the sample in the inner container is applied,breaching the inner container and releasing volatiles into the nowexposed outer container. Such materials can then be subjected to furtheranalysis in accordance with the inventive methods described herein withlittle risk of interference from substances in air, etc.

The rapid purging of air from the sample, and rapid replacement withargon or other gas prior to crushing the sample can be particularlyrelevant in analyzing samples relevant to oil and/or gas exploration.Generally, these methods are applied to older samples maintained underopen conditions, as there is a trade-off in terms of loss of volatilesubstances in applying the purging methods. Thus, for sealed samples,such methods may not be practiced.

Purging (and purging and replacing processes) can facilitate the massspectrometer analyses of very small amounts of certain substances, suchas methane, using mass 15 for the CH₃ ⁺ion, by removing nitrogen andoxygen. The lower resolution of many quadrupole mass spectrometers makesit difficult to analyze trace methane using mass 15 in the presence ofmajor amounts of nitrogen with a major peak on mass 14 and oxygen with amajor peak on mass 16. Purging and replacement of air with other gasesmay have other benefits. Replacement of air with krypton, having mass86, would solve the methane interference issue as does argon, but couldalso aid in the extraction of some recalcitrant volatiles in the solidby imparting a much greater amount of energy in collision with thelighter gases present as the sample's voids are evacuated.

Most purging steps are completed quickly, especially when the stepcomprises the removal of air in the system by means of quick vacuum(versus flowing of an inert gas or a combination of both types ofsteps). For example, in one aspect the purging process is complete inabout 10 seconds or less, such as about 5 seconds or less, about 3seconds or less, or even about 2 seconds or less. In the case of a quickvacuum purge, application of such a step for less than about 3 seconds,such as less than about 2 seconds, less than about 1.5 seconds, or even1 second or less can be advantageous. Another way to characterize such astep in some aspects is that the vacuum purge step results in a loss ofless than about 5%, less than about 2%, less than about 1%, or evenlower losses (e.g., less than about 0.5%) of the oil and with respect togasses the losses are less than about 10%, less than about 7.5%, lessthan about 5%, less than about 3%, or less than about 1% of the gaspresent at the time the sample is introduced to the system. Purging istypically performed prior to crushing or squeezing of materials, orother application of forces to the sample. At the well site, samples maynot be purged as nearly all information can be converted into data,especially with the use of control sampling devices/systems that areused to calibrate the system (with respect to gasses that are at thesite and not associated with the samples). For sealed samples, themethod also may lack purging, as this may result in data loss. As such,purging steps are often optional, but can be useful when there is adetermination that there could be a risk of an interfering signal.

Depending on the problem being addressed by the analytical method, italso or alternatively may be advantageous to heat or cool the sampleprior to volatile extraction. Heating or cooling of the sample can beperformed alone or with crushing and/or purging (or purging andreplacing the air or other surrounding gas). For instance, if volatilesin water ice were to be analyzed, the sample would need to be held at acold enough temperature to keep the ice frozen during volatileextraction and any purging and gas exchange for air preceding crushing.A temperature of about minus 50 degrees Centigrade might be needed inthis example to keep the ice from sublimating in response to the appliedvacuum. A similar process could be advantageous in the analysis of gashydrates, otherwise known as clathrates.

Centrifuging also or alternatively can sometimes be an aid to volatileextraction. Centrifuging an upright sample prior to volatile extraction,for example, can cause the vertical stratification of volatiles in thecontainer, gases would migrate to the top, and oil would in general forma layer on top of water. This can be particularly useful in the analysesof volatiles in drilling muds from oil and gas exploration andproduction wells. Centrifuging following crushing can sometimes alsohave similar advantageous effects.

After all preparatory processes, if any, are complete the volatilestypically are extracted from the sample by reducing pressure on thesample by exposing the sample container to an inlet system that is understatic vacuum and is not being actively pumped. The inlet systemtypically is sealed off to vacuum pumps at this point in the process,having been previously evacuated by vacuum pumps. Pressure is reduced onthe sample by opening a valve between the sample container and the inletsystem allowing gas to pass from the sample through the needle or otherflow channel device into the inlet system. During a multi-stageextraction, at increasing levels of vacuum for each extraction, thefirst extraction results in a resulting pressure on the sample and inthe inlet system that is determined by the gas pressure in the sampleand the sample container, the void volume in the sample container, andthe volume of the static inlet system. Each collection of extractedgas(ses) obtained by such a method is referred to as an “aliquot”herein. Thus, for example, the first extraction of a gas at atmosphericpressure or a different pressure may be referred to as Aliquot 1, withsubsequent aliquot numbers each increasing by one, so that a three stageanalyses will have Aliquot 1, Aliquot 2, and Aliquot 3. In typicalpractice, Aliquot 1 is extracted at a pressure of about 50 millibars. Atypical Aliquot 2 is extracted at an initial pressure of about 5millibars, and this pressure for a typical Aliquot 2 is decreased by aperiod of active pumping following initial trapping of the more volatilegases to about 0.001 millibars or less (e.g., as low as 0.0001 millibarsor lower, or any range between about 0.001 millibars and 0.0001millibars, such as 0.005-0.0005, 0.00075-0.00025, or 0.0009-0.0002millibars). The step of causing this significant type of pressure dropin the system, device, or method of the invention is advantageous inmethods in which a mass spectrometry analysis is performed on thesamples, as mass spectrometry conditions typically require lowerpressures than those in which aliquot extraction methods are performedin order to appropriately operate. Such pressure conditions will beknown in the art (or provided by the mass spectrometry manufacturer) andthe achievement of such levels of pressure can be achieved through anysuitable means, with many such methods and devices being available.

As mentioned elsewhere, the methods of the invention can, in certaininstances, include one or more steps in which potentially interferinggasses are removed from the released gas or the environment in which thegas is released. For example, in one aspect the invention can includethe step of flooding the device in which the method is performed with aninert gas such as argon, so as to remove gasses from the device, whichmight provide false signals or results. Normal atmospheric gasses suchas oxygen, nitrogen, and/or both, for example, can be substantiallyremoved, or nearly completely removed, or even entirely removed (todetectable levels) by administering (“flooding”) to the device or aportion of the device in which the method is carried out with such aninert gas. Such a method also can be used as a method for refreshing thedevice between samples. Where an inert gas is used in such aspects, theinert gas can be any suitable gas that does not chemically react withthe sample and does not cause any interferences with the chemicalanalyses of the samples' volatiles. In other aspects, a non-gaseousmaterial, such as a liquid can be similarly used. The atmospheric orother interfering gas can be purged from the device, component, orenvironment in which the sample is being analyzed by, e.g., rapid vacuumextraction (e.g., applying a vacuum that is sufficiently strong tosubstantially or nearly entirely remove the purging inert gas for aduration of about 1 second or less). In another aspect, the method cancomprise flowing an inert gas through the sample container or area todisplace the potentially interfering gas. Such methods are not includedin every application of the inventive methods. For example, where themethod is performed on samples sealed at a collection site, such as awell site, such a step is typically not performed. However, such purgingsteps can be useful for analyzing the presence of target substanceswhere such substances are or are suspected to be present only in verysmall amounts, such as with respect to methane and/or helium in samplesthat are associated with petroleum production or exploration sites.

Materials or methods also or alternatively can be used for removingother potentially interfering substances such as water vapor, forexample, which is relevant to certain aspects of the invention in whichwater is formed and analyzed as a method for analyzing hydrocarboncontent in samples. In one aspect, the invention is performed in thepresence of a material that can capture essentially all, substantiallyall, or a relevant portion of the water vapor present around the samplethat might be captured by either the trap or other tools for capturingsubstances used in the analytical method. For example, the system thatis used for performing the method can comprise passages between systemelements that are made of stainless steel, which promotes the absorptionof water and thus removes water vapor contained in the gas contentflowing through the system from reaching the next stage of the system.

The amount of volatile substances released from the sample, trapped onthe trap, or analyzed by the analytical method of the inventive methodsdescribed herein can constitute any suitable proportion of the volatilespresent in the sample, and the amount contained at each such stage ineach of the aliquots obtained in multi-aliquot methods of the inventionalso can be any suitable amounts. Typically, most of the volatiles arecaptured by the method, such that at least about 90%, at least about95%, at least about 97%, at least about 99% of the volatiles (excludingwater, and particularly with respect to C1-C10 hydrocarbons andsimilarly structured organic compounds) are extracted from the sample,by the practice of the methods of the invention. The efficiency of thesystem typically also is high with respect to trapping of gasses thatare condensable on the trap. Typically, condensable gasses that can becaptured by the trap are not retained in the system in detectablelevels. However, as discussed elsewhere herein certain gasses will notcondense on the trap or otherwise be trapped by the trap and must besubject to handling by other means to be captured and analyzed by themethod.

To exemplify (and clarify), methods of the invention can compriseanalysis of a single aliquot, for example a single aliquot obtainedunder gentle/low vacuum conditions, or in other aspects the method cancomprise obtaining and analyzing a plurality of aliquots from one ormore samples and/or that are obtained under different conditions. Forexample, one method comprises obtaining two aliquots per sample, whereinthe first aliquot is obtained by application of about 50 millibars(e.g., 10-100 millibars, such as 15-95 millibars, 20-90 millibars, 30-80millibars, or 40-70 millibars) for about 3 minutes (e.g., 1-10 minutes,such as 1.5-8 minutes, 2-7.5 minutes, 2.5-5 minutes, or the like, insome cases it may be advantageous to perform the first aliquotextraction for shorter times in this or other contexts, such as 0.25-4minutes, 0.33-3.5 minutes, 0.5-3 minutes, 0.5-4 minutes, 0.5-5 minutes,0.5-2.5 minutes, 0.5-2 minutes, 0.75-3 minutes, 0.75-2.5 minutes, 0.75-2minutes, or another similar time interval) and a obtaining a secondaliquot by putting the sample under pressure conditions of about 5millibars (e.g., about 1-10 millibars, about 2-8 millibars, about 3-7millibars, or the like) for a period of about 10 minutes (such as 5-15minutes, e.g., 6-12 minutes, 6-10 minutes, 5-9 minutes, 6-9 minutes, 7-9minutes, 7-10 minutes, or about 7 minutes, about 8 minutes, or about 9minutes), with the method optionally including a step ofcrushing/squeezing the sample during one or both aliquots, such ascrushing the sample at the start of the first aliquot extraction, asdescribed elsewhere herein. In some aspects, shorter extraction times(e.g., less than about 5 minutes, less than about 4.5 minutes, less thanabout 4 minutes, less than about 3 minutes, less than about 2.5 minutes,less than about 2 minutes, less than about 1.5 minutes, less than about1 minute, or even shorter periods. In such aspects the parameters of thesystem and the method can be adjusted to facilitate shorter extractiontime, such as, for example, using a relatively larger diameter needlesystem for the passage of volatiles out of a punctured sample container(e.g., use of a needle of about ⅛th or about 1/16th of an inch internaldiameter as compared to about a 32nd of an inch diameter needle). Inanother approach, extraction time and/or purging time of the system canbe reduced by to passing a non-condensable purge gas through the sample.

In some contexts, it may be useful that the method of the invention isperformed and/or the device of the invention is provided with aplurality of trapping devices, which may be of the same or differentnature. Thus, for example, in one aspect, the invention includes aplurality of non-selective traps, such as a plurality of liquid nitrogentraps. This kind of system/device can be particularly advantageous withmultiple aliquot methods. In such methods it can be possible that eachaliquot or at least a subset of the total number of aliquots areassociated with each trap. This can, among other things, speed up theprocess of performing multiple aliquot analyses, for example by exposingthe aliquots to the traps separately or operating traps at differenttimes, such that there is little downtime in the system in the event atrap needs to be cleaned, set, or re-set in between uses. Where trapswith different functional properties are provided, using different trapscan enhance the information obtained from the method, by providingdifferent dimensions to the analysis (e.g., by combining one or morenon-selective traps with one or more selective traps, such as GC traps).

As already noted, gasses released from the sample are released to asystem or device in which the remaining steps of the method areperformed. Typically, the gasses pass into the system or device throughan inlet, which may be a portion of the system or device associated witha needle or flow channel as discussed elsewhere herein or can be anyother suitable type of inlet. Thus, processes employed before and duringvacuum extraction can include attaching the sample container to theinlet system before initiation of vacuum extraction and any ancillaryprocesses. A number of processes can be used to attach the samplecontainer to the inlet system. These are described in the section on thevarious possible configurations of the sample container. Our preferredsample container is a sealed brass tube with a hermetically attachednitrile cap on the top and a neoprene plug in the bottom. Using thetypically preferred sample container, the sample container is attachedto the inlet system prior to initiation of vacuum extraction by passinga needle through the nitrile cap. Other types of sample containers mustbe sealed by other appropriate means to the inlet system prior toinitiation of vacuum extraction.

Another step of the inventive methods also or alternatively can includeapplying energy to either the gasses generated in the practice of theinventive methods, which can include either gasses directly releasedfrom the sample or gasses that are released from the trapping device ormedia of the invention (the “trap”, as further described elsewhereherein). The amount of energy and type of energy applied to gasses insuch aspects can be in any suitable amount and form so as to generateone or more other target substances that, for example, are moreconvenient for detection and/or analysis than substances that were inthe gasses prior to application of the energy. For example, the methodsof the invention can comprise a step of applying an energy source suchas a source of light energy to a gas, thereby forming compounds fromorganic acids, such as carbon monoxide, water, carbon dioxide, methane,and the like, in amounts that are suitable for detection by theanalytical aspects of the inventive methods. Carbon monoxide often ispreferred as a molecule for detection in that it typically lackspotential competing signals which may sometimes pose issues foranalyzing water or carbon dioxide. Carbon monoxide is generated by thebreakdown of formic acid (HCOOH) to water (H2O) and carbon monoxide(CO). This reaction even occurs at about 1 atmosphere pressures, so muchso that some large bottles of formic acid are provided with a vent thatallows carbon monoxide to escape and thus avoid unwanted pressure buildup in the bottle. In contrast, acetic acid (CH3COOH) breaks down towater (H2O) plus methane (CH4), and carbonic acid (H2CO3) breaks down towater (H2O) plus carbon dioxide (CO2). Carbonic acid is only stable insolution, and has no stable gaseous phase.

The amounts of organic acids released from materials, such as cuttings,may be very small, and their respective indicator break down compoundsmay be masked by larger amounts of these compounds being released ascompounds existing as those compounds in the sample. In geologic samplesthis is especially true for water, carbon dioxide, and methane. This isnot a usual problem for carbon monoxide as its natural occurrence insamples from oil and gas wells is minimal at best. However, carbonmonoxide can be generated as a by-product of oil and gas drilling by theprocess known as “bit burn” or “drill bit metamorphism”. In a labapparatus aspect of the invention, and related methods of use, some ofthe compounds derived from organic acids that are also present asnaturally occurring interfering compounds, such as water and carbondioxide, are frozen to a liquid nitrogen (LN2) trap. Carbon monoxide andmethane do not freeze to the LN2 trap. However, methane as a naturallyoccurring substance is common in rocks from oil and gas wells.Therefore, the presence and amount of methane in rocks from oil and gaswells is not an adequate indicator of precursor organic acids. Carbonmonoxide is not at all common as a natural component of rocks from oiland gas wells. Therefore, the presence of carbon monoxide typically is agood indicator of organic acids. Thus, for example, in one set ofaspects the inventive methods comprise detection of carbon monoxide, butnot methane or at least do not comprise relating methane levels tooverall levels of organic acids in the material associated with thesample/cuttings.

In certain aspects, carbon monoxide is monitored using the AMU12fragment formed by mass spectrometry analysis of carbon monoxide. In amore particular aspect, the method comprises performing a method inwhich carbon monoxide is a primary indicator of organic acids in thematerial, and is analyzed by evaluating the presence and amount of theAMU12 fragment formed by mass spectrometry performed on carbon monoxide,and the method is performed either free of any detectable amount ofcarbon dioxide or in the presence of an amount of carbon monoxide thatdoes not result in a distortion of the carbon monoxide-associated AMU12signal or the degree of the AMU12 signal that is associated with carbonmonoxide. In some aspects, the amount of interference with the AMU12signal from the presence of carbon dioxide in such a method is less than25%, less than 20%, less than 15%, less than 10%, less than 5%, lessthan 2%, or less than 1%. In settings where carbon dioxide is present,the method can comprise either manually or automatically correcting theAMU12 signal data for the presence of carbon dioxide to obtain a carbonmonoxide-associated AMU12 signal. In some aspects, the step of isolatingcarbon dioxide is handled by use of a trap that collects carbon dioxide,such as a liquid nitrogen trap, in a manner such that carbon monoxideand carbon dioxide are not in associated aliquots (for example, carbonmonoxide in a lab device of the invention may be collected in anon-condensable gas state, whereas carbon dioxide is fixed to the liquidnitrogen trap). In other aspects the method of analyzing carbon monoxidelevel also or alternatively comprises analyzing the signal from AMU13and/or AMU 16 and/or 28. In aspects where carbon dioxide is initiallypresent but removed or substantially removed (e.g., by removal of atleast 85%, at least 90%, at least 95%, at least 97%, at least 99%, ormore, of the initial concentration) as a part of the inventive method, aCO2 absorber, such as Decarbite™, also or alternatively can be used toreduce or eliminate any detectable levels of carbon monoxide in the gasor aliquot to be analyzed, Also or alternatively, a mass spectrometerbased machine designed to detect trace amounts of carbon monoxide incuttings can be designed to use any of the CO2 eliminating/reductiontechniques described herein and their known equivalents in the art.

In another aspect, the method is performed under conditions in which theapplication of the energy also or alternative changes the pressure ofgas associated with the sample or generated from the sample in a manneror amount that is indicative of a chemical change that identifies thepresence of a target substance or a target-related substance (such ascarbon monoxide).

It is important to note that while in many aspects of the inventivemethods mass spectrometry analysis is an important component of theinventive method, such a step is not always included (and often is notincluded) in these methods. Rather, other analytical steps can beperformed to identify the presence of the target substance ortarget-related substance. For example, a carbon monoxide meter ormeasuring device can be used to directly measure the formation of carbonmonoxide in a petroleum-related sample, thereby indicating the presenceof organic acids prior to application of the energy, and thereby furtherindicating the presence of oil-related substances in the sample (andmaterial). Also or alternatively, simply measuring the pressure in thegas related to the sample can be indicative of a relevant change, suchthat a pressure gauge, meter, or device can be used in the method, aloneor in combination with mass spectrometry analysis (carbon monoxidemonitoring also can be combined with mass spectrometry analysis or allthree methods can be combined in the analytical method).

Such methods of the invention also can often be desirably performed inthe field, such as directly at a well or exploration site. Accordingly,whereas many aspects of the invention comprise the use of small samples,in these and other methods larger amounts of materials may be used, suchas cup sized containers, pint size containers, quart size containers,gallon size containers, or containers that have volumes of about 5liters or more, about 10 liters or more, about 20 liters or more, oreven about 30, 40, or 50 liters or more (e.g., a large bucket of samplematerial). For example, a large container of cuttings can be collectedfrom where cuttings are deposited near a well site (e.g., in associationwith a well site shaker table) and then directly used for analysis withsuch methods.

In addition to or alternatively to light energy, other suitable types ofenergy can be applied to the sample in order to modify the gas contentfor direct evaluation or to see if pressure increases, indicating achange in content that is indicative of the presence of the targetsubstance in the material. Examples of other types of suitable energyinclude heating methods, vacuum, other forms of radiation (e.g., UVlight), and the like. In another aspect, the method also oralternatively can comprise performing a chemical reaction to form suchcompounds that are indicative of the presence of the target substance inthe material. The amount of energy applied in practice of the method canbe any suitable amount to achieve the desired change. In one exemplaryaspect, the sample is heated to about 400 degrees C. or greater for aperiod sufficient to generate indicative target compounds (e.g., carbonmonoxide) from organic acids present in the samples.

Methods of the invention can and often do include the step of subjectinga sample of the material, such as one or more cuttings associated withone or more geologic formations, to one or more forces to cause therelease of a first gas containing an analyzable amount of one or morevolatile substances. The force that can be applied to the sample caninclude a pressure force, such as a high pressure (positive pressure) ora vacuum; temperature; chemical reaction; application of radiation (suchas microwave, which might be used to remove water from material); and/orphysical forces, such as crushing or vibration (e.g., ultrasonicvibration). Other forces that can be applied include dehydrating thesample by heat or chemical means, applying temperature to the sample,applying mechanical pressure on the sample, mechanically rupturing someor all the sample, subjecting the sample to a chemical reaction, or acombination of any or all thereof, optionally in addition to applyingone or more levels of vacuum and/or pressure to the sample.

In one aspect, the force is a vacuum pressure, such as the vacuumpressures described above. For example, a low pressure can be applied toa sample of the material as a means for causing one or more volatilesubstances to be detectably released from the material (or a vacuum canbe applied that would increase the release of one or more volatilesubstances or gas(ses) from the sample if such a volatile substance ispresent). The precise amount of vacuum will vary depending on thematerial and other conditions of the method. Commonly the pressure willbe below atmospheric pressure but greater than about 3×10−4 millibars.In another aspect, practicing a method of the invention comprisesapplying a vacuum to the sample at a pressure that is betweenatmospheric pressure and about 1×10−3 millibars. In yet another aspect,the method comprises applying a vacuum to the sample at a pressure thatis between atmospheric pressure and about 25×10−3 millibars. In stillanother facet, practicing a method of the invention comprises applying avacuum to the sample at a pressure that is between atmospheric pressureand about 1×10−3 millibars. In yet another aspect, the method comprisesapplying a vacuum to the sample at a pressure that is betweenatmospheric pressure and about 1×10−2 millibars. In still another sense,methods of the invention can comprise a step of applying a vacuum to thesample that is defined by a pressure of between about 1 to about 100millibars.

In other particular aspects, the method comprises applying a positivepressure to the sample. A positive pressure can be any pressure that isin excess of ambient atmospheric pressure and that results in ameasurable release of desired gas(ses) (at least under conditions inwhich volatile substances that form such gas(ses) are present in thesample). Positive pressure can be applied by any suitable means, suchas, for example, using a piston. The method can include one or moreapplications of positive pressure, or the combination of application ofpositive pressure with any of the other methods described herein foraiding disrupting the sample and/or extracting fluids from the sample.The specific pressure applied will depend on the other conditions of themethod, such as the nature of the material and whether other forces areapplied to the sample. In one example, a pressure of about 400 to about4000 pounds is exerted on the sample (e.g., about 1000 pounds to about3500 pounds), although higher pressures also can be exerted by usingcertain methods available in the art, such as hydraulic pistons.

In another aspect, the method also or alternatively includes applicationof a physical force, such as crushing, abrasion, thermal decrepitation,grinding, and/or drilling. For example, materials can be loaded into asample container comprising a crushable portion, such as a crushablesidewall, and the sample container can be subjected to crushing so as topromote the release of volatile materials. For example, as discussedelsewhere herein, samples that are or that comprise cuttings can includehydrocarbon materials contained in small fissures, pores, and otherstructures, which are distinguishable from fluid inclusions, by theirexposure to the environment and/or in that they are characterized in notbeing hermetically sealed in an inclusion. These formations ingeological material, which are also represented in cuttings taken fromsuch material, can contain hydrocarbons, such as petroleum-relatedhydrocarbons, which are held in the geologic material. Application of aphysical force, such as crushing, can assist in releasing such materialsfrom such formations. Selection of the parameters for these methods willvary with the nature of the material, other parts of the analyticalmethod, etc. A typical exemplary method of the invention will comprisecrushing samples, such as cuttings, by about 400 pounds to about 4000pounds, which can be achieved using some of the exemplary devicesdescribed herein.

It should be noted that in certain aspects of the invention no force isapplied to the sample. In other words, just the exposure of the materialto a release channel, such as a needle that penetrates a container inwhich a sample of the material is contained, can allow the gas to beexposed for performance of the next step of the method or to flow toeither another container, portion of a device of the invention, or thelike, wherein such other steps can be performed. For example, in oneaspect, the gas that is released from the sample will flow to a gas trapdevice, such as a liquid nitrogen gas trap, such that a portion of thegas becomes trapped in the trap and thereafter can be released in apredictable manner.

In one embodiment, methods of the invention are characterized by thecollection of the sample in a sealed container and by the subjecting thesample for an initial period to approximately the same pressure (e.g.,within 90%, 95%, 99%, or more of the same condition) or exactly the samepressure (at least within limits of detection and/or condition, such asat atmospheric pressure without respect to natural fluctuations in suchpressure) at which the sample was sealed in the sample container, suchthat a majority of the volatile materials are not lost when releasedfrom the container. Often this means that the sample will initially besubjected to atmospheric pressure.

In another aspect, in addition or alternative to crushing the sample, bythe methods described elsewhere herein the methods can comprisemechanically rupturing some or all of the sample, subjecting the sampleto a chemical reaction, or performing a combination of any thereof,alone or in combination with application of crushing, compression, orthe like. In another facet of the invention it is characterized by thelack of any step that comprises application of heat (e.g., an increaseof temperature of about 25% or more, about 35% or more, about 50% ormore, about 75% or more, about 100% or more, etc.) for a period of morethan about 12 hours, such as more than about 6 hours, more than about 4hours, or more than about 2 hours.

In one aspect of the invention the method comprises isolating or“trapping” some portion of the gas released from the sample bycontacting the released gas with a “gas trap” (which may also simply becalled “a trap”).

“Trapping” means that the trapped gas is collected and maintained orheld in a device, medium, and/or location. Trapping in the context ofthese aspects of the invention typically occurs in a releasable manner,and commonly the gas is trapped in a manner such that parts of thetrapped gas can be released from the trap in a predictable manner, suchas when some kind of change is made to the condition of the trap. Forexample, in one aspect the trap is a material that bonds to some portionof the gas and the gas is released by changing the conditions of thebonding, for example, by increasing the temperature.

In a preferred aspect, the trap is a cryogenic trap, such as a liquidnitrogen trap, which traps gasses through freezing of volatile compoundsonto a surface that has been cooled by liquid nitrogen or othercryogenic methods thereby freezing the volatile compound to the trapdevice or trap media. In such embodiments, the method can include thestep of releasing of volatile compounds from the trap due to warming ofthe trap, thereby releasing volatile compounds from the trap in apredictable sequence for further analysis and/or treatment. Freezingtraps can be operated under any suitable conditions. Typically,conditions will be selected based on the properties of the material tobe trapped by the media or device used in the inventive method. In oneaspect, the trap is a material or device that is cooled to about minus50 degrees C. or less in the performance of the method (e.g., aboutminus 100 degrees C. or less, such as about minus 150 degrees C. orless, such as about minus 190-200 degrees C., although in some casescolder temperatures can be obtained and employed). Commonly, thecryogenic trap will be cooled to such a temperature prior to theexposure of the gas released from the sample to the trap. In thisrespect, as in some of the preferred devices described below forpracticing the inventive methods, there may be one or more controllablevalves that are used to controllably expose the sample-release gas tothe trap, and the method correspondingly will include the step ofexposing the trap to the sample-release gas in a controllable manner,after such cryogenic cooling.

Other types of traps may also be suitable for performing steps of theinventive methods. In one case the trap may be selective, in that it iseither capable (or more capable) of selectively binding to certainmaterials and/or selectively not binding certain materials. In one case,for example, the trap is selected such that it is selective for nottrapping water, carbon dioxide (or other compounds that might interferewith parts of the analysis, make analysis more difficult and/or lessaccurate), and/or make analysis take longer or cost more) and/or one ormore organic acids, particularly if analysis of the organic acids isalso a part of the method.

Typically, however, the trap used in the inventive method is anon-selective trap, at least with respect to target substances ofinterest. The term “non-selective trap” in the context of this inventiontypically means that the trap binds to all or substantially all of thevolatile compounds present in the sample or all of the relevant volatilecompounds that are present in the sample. The operation of such anon-selective trap can be contrasted with a selective trap, such as maybe found in a gas chromatograph (“GC”), which binds to a certaincompound or a class of compounds, but does not bind to other compounds.This is not to exclude application of GC technology in performingcertain aspects of the invention, as aspects of the invention in whichGC technology is used are described elsewhere herein and, as notedabove, in certain cases selective traps, such as using a GC material (orset of such materials), could be part of a trap component of theinvention, or could constitute the trap.

In aspects where the gas is subject to a trap, the material contained inor that is otherwise bound to the trap can be considered to form an“aliquot” that is used for further analysis according to various aspectsof the invention.

As noted above, gas trapping devices, media, or systems, which can beused in various contexts of the invention, can be either selective ornon-selective. In one aspect, the gas trapping device is a non-selectivetrap, capable of capturing gas containing a number of different types ofvolatile compounds, such as a cryogenic trap which freezes volatilecompounds to fix them to a media. A liquid nitrogen trap is an exampleof such a cryogenic trap.

The gas released from the sample (or “first gas”) will be allowed tocontact the trap for any suitable period of time. The optimal time ofcontact will vary with the trap, the gasses that are present or expectedto be present, and other factors. For cryogenic traps, such as theliquid nitrogen trap described above, the time of contact between thetrap and the volatile substances can be relatively short, such as lessthan about a minute, and commonly less than about 45 seconds, usuallyless than about 30 seconds, and often as little as about 15 seconds,about 10 seconds, or less than about 10 seconds (such as 7, 6, or even 5seconds) will be suitable. In certain cases, the trap will comprise apumping function, such as in the case where the trap is a cryogenictrap/pump, which may occur by the action of freezing substances to thetrap. In this respect, having conditions that cause freezing quickly canbe important, as such quick freezing removes volatile compounds from theatmosphere surrounding the sample, which will, in turn, cause morevolatile compounds to be released from the sample (as the system workstowards equilibrium).

However, the entire period that gasses released from the sample areexposed to the trap will be significantly longer than these shortperiods, such as a period of about 10 minutes or longer, for exampleabout 15 minutes or longer, about 20 minutes or longer, about 30 minutesor longer, about 40 minutes or longer, or about 60 minutes or longer.The amount of time of exposure depends on the pressure applied, thenature of the sample, and other factors. When, for example, seeking torelease and analyze more refractory substance in the sample and/or whendealing with a particularly difficult sample material, longer times ofapplication may be required, such as about 15 to about 30 minutes.However, in other aspects, the amount of time that is applied is about10 minutes or less, such as about 8 minutes or less, about 6 minutes orless, or even about 5 minutes or less.

In some cases, where the method is performed with repeated cycles, thecycles can vary in terms of the amount of time in which gas is exposedto the trap. For example, in the first cycle of a method the time may berelatively shorter, such as less than about 10 minutes, where there maybe more gas readily available in association with the cycle, whereas insubsequent cycles, where it is more difficult to extract gas from thesample, a longer period of time may be employed, such as about 10minutes or longer, so as to permit the second cycle gasses tosufficiently bind to the trap.

In aspects in which an extended time prior to the warming of the liquidnitrogen trap is provided, the extended time is not solely to providemore time for the gasses to bind to the liquid nitrogen trap, but,rather, such an extended time can provide for improved extraction orliberation of volatile species from the sample. Thus, the liberation ofvolatile gasses from a sample can be, at least in some respects,considered to depend on the variables of the nature of the sample, thenature of the volatiles, the forces applied on the sample to promoterelease of such volatiles, and the time given to permit such releaseand/or collection of gasses. It is often preferred that all volatilefluids that are gaseous in the sample are collected prior to exposure toany vacuum. Where the sample contains volatile liquids, the applicationof vacuum to the sample, such as after “passive” (non-vacuum) collectionof gaseous volatile substances from the sample, can be desired, inasmuchas such application of vacuum may lead to boiling of substantially allor all of such liquids, or at least result in the boiling of asubstantial proportion of such volatile substances (at least 20%, atleast 30%, or at least 33% of the amount); a majority of the substances;a substantial majority of the substances (at least 66.66%, at least 75%,at least 90%, at least 95%, at least 99%); or at least a detectableamount of such substances. In any case, the boiling of such volatilesthat are normally liquid (at atmospheric pressure and typical ambienttemperature) will render such boiled substances or boiled fraction ofsuch substances gaseous. The length of time required to achieve adesired level of boiling of liquid substances in the sample is dependenton factors similar to those described above with respect to release ofgaseous volatile compounds, but will primarily depend on the weight ofthe substance (heavier materials typically require longer to boil).Application of longer periods of vacuum, and resultant boiling, can,thus, result in the conversion of a significant amount of liquidvolatiles into gaseous species for analysis in accordance with theinventive methods described herein. Thus, the certain aspects of theinvention that comprise application of extended periods of time forrelease of gaseous volatile substances from a sample and/or applicationof vacuum to boil liquid volatile compounds in a sample provide theinventive methods a unique advantage over the prior art in that more ofthe volatile substances in a sample can be fully analyzed by allowingthe time required for more of the volatile liquids to be released and/orcaptured.

In one aspect of the method, the change in temperature used to releasegas species from the liquid nitrogen trap is performed in less time thanflash warming methods used in gas chromatograph (GC) methods that alsouse liquid nitrogen trapping. Such GC methods use “flash” or rapidwarming applied to a liquid nitrogen trap used in the GC method, whichrelease many, most, or substantially all of the gasses trapped to theliquid nitrogen trap at once. GC methods also require that all of thegasses to be analyzed enter the GC media simultaneously, such as a trapif used in the method, nearly simultaneously, as the presence of all ofthe gasses to be analyzed at the same time is necessary for theeffective performance of such analytical methods. These limitations aretypically not required (or desired) for the inventive methods describedherein, and as described elsewhere a gradual warming of the liquidnitrogen trap over a more sustained period of time to permit for thepredictable release of trapped gasses is a common aspect of methods ofthe invention that comprise a trap, such as a liquid nitrogen trap.Also, this negates the need for any kind of separation of gasses otherthan the warming of the liquid nitrogen trap in these aspects of theinvention. Thus, in another facet of the invention, the invention lacksany step of molecular selection, such as molecular distillation orsimilar method, being performed on the substances to be analyzed in themethod.

In some aspects, a relatively high vacuum can be applied to a trap orapplied in the device or system used to carry out the inventive methodsuch that the trap is under vacuum conditions for a period of time. Forexample, in some cases where a relatively high vacuum is applied to asample that vacuum also may be applied through other parts of thesystem, including the trap. In other aspects, the method also oralternatively comprises a method in which vacuum is applied to capturenon-condensable gasses and remove such material from contact with thetrap (or to at least substantially achieve such a state).

In certain aspects, such as where relatively high vacuum is applied tothe trap or in the system such that a vacuum condition is present at thetrap for a period, it can be advantageous to continue to reinforce thetrap media or device with whatever substance is used to trap the targetgasses, such that gasses that might be easily/readily released from thetrap are maintained in contact with the trap. For example, in the caseof a liquid nitrogen trap the method can comprise continuously applyingliquid nitrogen to the trap while the vacuum condition is present so asto retain substance of interest (e.g., ethane, ethene, etc.) trappedinto the trap until they are ready for release in a predictable manner.

Another action that can form part of the methods of the invention is thestep of isolating the aliquot from the sample. Commonly, once gasses arecollected from the sample to form an aliquot, that aliquot can then beisolated from the sample, such that the remainder of the analysis of themethod or at least that step or part of the method is conducted on thealiquot without further collection of gas from the sample for thecollection of the present aliquot (or if this is the final aliquot oronly a single aliquot is being collected for the particular applicationof the method). This method of isolating can be performed for manyreasons and using any suitable technique. Where devices of the inventiondescribed elsewhere herein are used in the practice of the method, forexample, one or more valves may be engaged, which results in isolatingthe gas of the aliquot from the sample. The method also or alternativelycan include the step of isolating the trapped gasses from access toother components of the device or system in which the trap is situated.For example, where the method is performed with a device of theinvention that comprises (a) a sample holding unit, (b) a gas trap, and(c) a mass spectrometer, the method typically will comprise the step ofisolating the gas trap from both the sample holding unit and the massspectrometer for one or more periods of time (e.g., isolating the trapfrom the samples after a sufficient passage of time and/or applicationof conditions necessary to collect gasses from the sample and isolatingthe mass spectrometer until it is time to release the gasses from thetrap to it for analysis).

In aspects of the invention in which one or more gasses released fromthe sample are subjected to a trap to form an aliquot, the methodtypically includes the step of releasing volatile substances from thealiquot as trap-released gasses in a predictable sequence. For example,where the sample is comprised of one or more drill cuttings obtainedfrom an oil well site, gas is obtained from cuttings, either passivelyor by the application of one or more forces, such as mechanical crushingand/or application of one or more vacuum pressures on the sample, andthen subjected to a trap, such as a liquid nitrogen trap. Much of thegas from the cutting samples will be captured by the trap. Allowing thetrap to heat, either passively, or, more typically through theapplication of heat, directly or indirectly, to the trap, will allow forvolatile substances in the gas that are frozen to the trap to bereleased in a predictable manner.

A “predictable manner” means that substances such as individual volatilegasses or mixtures or other types of volatile gas species are releasedfrom the trap in a manner such that if gasses are present their releasecan be predicted from the timing and/or condition of their release. Forexample, in one aspect a predictable manner means that different speciesare released as a function of time. In many aspects, the release ofspecies can overlap the release of other species, such that, forexample, there may be first period of release of one or more firstspecies (e.g., lighter or more volatile compounds), a second period inwhich there is a release of one or more second species (e.g., heavier orless volatile compounds), and an intervening period in which both theone or more first species and one or more second species are both beingreleased. In many aspects, there will be several such periods andintervening periods. The periods and intervening periods may, however,form a predictable pattern of release such that if expected compoundsare present in the sample it will be known to expect them to release ata certain time and/or under the application of a certain condition.

Another step of the inventive methods also or alternatively analyzinggasses that are directly released from samples, typically after theapplication of an energy to the gas, to break down (decompose)substances in the gas, thereby turning volatile species in the gas totarget substances for analysis. For example, such a method of theinvention can comprise taking a volume of a sample, such as cuttings,optionally applying one or more forces to the sample so as to releaseone or more endogenous volatile gasses (such as formic acid, aceticacid, carbonic acid; or other organic acid), applying an energy sourceto volatile gasses so as to break down the volatile species to one ormore target compounds (such as carbon monoxide), and analyzing thetarget compounds to determine whether the endogenous volatile substanceswere present, particularly if the presence of such endogenous substancesare indicative of the presence of petroleum or another material that isdesired. In such methods, optionally no trapping of a gas is performedand/or no mass spectrometry or similar method is applied. This aspect ofthe invention provides simple methods that can be readily performed withlimited amounts of equipment, while still providing a sufficientindicator that petroleum or another target substance is in the relevantformation associated with the sample.

The amount of energy to be applied can be any suitable amount of energyand/or force to break down the volatile substances into the targetsubstances. In one aspect, the invention comprises applying heat ofabout 400 degrees C. or higher or another temperature or condition so asto disassociate formic acid, carbonic acid, or both (in one aspect,carbonic acid only) to one or more components thereof, such as carbonmonoxide and/or carbon dioxide. In another aspect, the method comprisesapplying a vacuum to the sample to assist or handle the breakdown of theendogenous volatile substances into the target gas(ses). Vacuumconditions described elsewhere herein have been associated with suchbreakdown of endogenous gasses and may be applied in this aspect aswell. In still another aspect, the invention also or alternativelycomprises contacting the sample with one or more chemicals that assistin the release of the target gasses from the endogenous gasses, such asapplication of a desiccant. Another aspect comprises application ofradiation, such as microwaves, to the sample, to aid with the breakdownof the endogenous gasses.

The methods of the invention also include the step of analyzing gassesgenerated or released in the various methods (e.g., trap-released gassesor decomposed gasses generated where no trapping is performed), so as todetermine if substances of interest are present in the formation ormaterial from which the sample was taken or with which the sample wasassociated. Any suitable type of analysis can be applied to such gassesand any suitable combination of methods can be applied as well, ifdesired and possible.

A preferred aspect of the inventive methods described herein comprisesthe application of mass spectrometry analysis to trap-released gasses.Any suitable type of mass spectrometry method can be used in thisrespect.

When performed in the practice of the invention, a mass spectrometrymethod typically will be selected to be suitable for the identificationof expected or desired target substances. For example, if the desiredtask is to identify the presence of petroleum-relevant hydrocarbonsand/or organic acids and/or inorganic gasses (e.g., H₂S, helium, andCO₂) in cuttings obtained from an oil well, the mass spectrometer willbe selected and operated such that it can identify, among other things,volatile gasses such as octanes, nonanes, and larger hydrocarbons thatare indicative of the presence of petroleum in the geological formationfrom which the cuttings originated. Mass spectrometry is typically apreferred method as it works rapidly and provides a useful, detailedlevel of analysis. There are a variety of mass spectrometry devices thatcan be used in performing methods involving mass spectrometry. Aquadrupole mass spectrometer (residual gas analyzers (RGAs)), forexample, are readily available devices, which might be suitable for manyof the methods described herein. Time of flight mass spectrometers,which provide rapid analysis, also may be suitable in many instances.More complex systems, such as mass spec/mass spec (dual massspectrometers/triple quads) also could be used in some cases and may beadvantageous for better resolving substances with masses that aresimilar to other substances which may be present.

Mass spectrometry is not a required component of the invention, however,as other analytical methods can be used to analyze samples in accordancewith the invention. Flame Ionization Detection could be used foranalysis of various hydrocarbon species. Gas chromatography also oralternatively can be used to analyze gasses in certain aspects of theinvention. It also or alternatively may be possible to analyzehydrocarbons via infrared spectroscopy or Raman spectroscopy.

Other times simpler methods can be used in the place of massspectrometry or such sophisticated methods, such as gas chromatography.In important aspects of the invention the invention comprises detectingthe formation of target substances which are released from organicacids, such as carbon dioxide or carbon monoxide, which can be detectedusing conventional, commercially available detection devices or thetechnology in such devices. Pressure release, for example, may also oralternatively be used as an indicator in some methods. Water releasecould simply be measured using a humidity meter, and also oralternatively provide relevant information in certain aspects of theinvention.

Although the methods of the invention can be performed with variousapproaches, in some aspects methods can be characterized by steps thatare not performed and/or the components that are absent from a device orsystem of the invention. For example, one aspect of the invention ischaracterized by the lack of any gas chromatography step in the method(or, correspondingly, by the lack of such device/component in thesystem/device of the invention). Other steps that may be excluded fromthe methods of the invention include infrared analysis. It will beunderstood that generally the principles described herein with respectto the methods of the invention will implicitly carry over to thedevices and systems of the invention, such that this description shouldalso be interpreted as disclosing devices and systems lacking infraredcapabilities.

In aspects of the invention where a trap is used, another optional stepof the inventive method is collection and analysis of non-condensablegasses (i.e., gasses that will not condense and securely bind to thetrap, and/or other materials from the sample) (“NCGs”). In some aspects,application of one or more other steps of the method may generatematerials that will not bind to the gas trap. For example, where aliquid nitrogen gas trap is used some materials may not be too volatileand/or some gasses may not bind the trap or at least not bind to thetrap completely or bind to the trap in sufficient quantities to indicatean accurate amount of the material or even to indicate the presence ofthe material at all in the sample. In such cases the method can includecollecting non-condensable materials and/or non-binding gasses. Thesematerials may be collected, such as by applying a collection method toisolate such material for later analysis. In the use of devices of theinvention, the device can include a mechanism for collecting suchmaterials in a manner that isolates them from the rest of the materialto be analyzed. A vacuum can be applied to gasses that are not bound bya trap, for example, to collect such gasses. Ideally such gasses areisolated and captured in a container or structure functioning as acontainer in a device and then selectively subjected to analysis beforeor after analysis of the trapped gasses. In some aspects, the NCGmaterial may be in too great a quantity for analysis and the method willcomprise a step of limiting the amount of NCG material that is analyzedand/or controlling the rate of analysis of the NCG material.

In some aspects, the methods of the invention can include the step ofrepeating various steps of the method. For example, in one aspect theinvention provides methods comprising a cycle of repeatedly applying oneor more forces to the sample to cause or assist in the release ofvolatile compounds from the sample. Such methods can include therepeated application of the same type of force or applications of two ormore different forces or the application of the same type of force butin a different amount, duration, etc. For example, in one aspect theinvention provides methods in which vacuum is applied to the sampleseveral times, at different pressures, for different periods, or both.In some aspects, gasses expected to contain certain volatiles under thiscondition are the target of one or more analytical methods practiced onthe gasses or on trapped gasses generated from the sample-releasedgasses. Such methods typically also will include multiple steps ofcapturing the multiple gas aliquots generated by application of themultiple forces, releasing such respective gasses, and analyzing suchreleased gasses, which can then be examined in combination to obtain aprofile for the sample.

Analysis of substances by the methods of the invention can bequalitative (determining the presence, but not the amount),quantitative, or both. Methods of the invention in which trapping andpredictable release of trapped gasses occur are particularly amenable toquantification. In one aspect, the invention provides a method that iscapable of quantifying the amount of one or more volatile compoundscontained in the sample. Quantification can be performed throughanalysis against a standard. For example, a standard of a gas at a knownvolume and known pressure can be generated and a sample can be comparedto this standard. Similarly, a drop of a liquid of known volume andcomposition can be analyzed by the method employed and then theresult(s) from the sample(s) compared to such a standard. Standardcompositions are typically comprised of a NCG, such as nitrogen (e.g.,at least about 80% is nitrogen or at least about 85%, at least about90%, or more of the standard is nitrogen and/or methane), with the smallremaining amount comprising a known amount of one or more hydrocarbons,which will be released from the trap at different temperatures, andallowing for quick analysis of the standard material. Because standardsmay not be contained in a material such a cutting the method maycomprise controlling the volume and/or rate of release of materialanalyzed (e.g., by using a needle or constricting passageway to controlthe flow of the sample material to the analytical components of thesystem).

Methods of the invention can comprise analyzing the sample for thepresence of organic acids and/or hydrocarbons, with the analysis of thepresence of organic acids (which typically is done by analyzing for thepresence of other target substances, such as carbon monoxide, whichindicate such organic acids are present) typically being preferred orselected if only one of the two are analyzed. Nonetheless, the analysisof hydrocarbons also can be important. For example, analysis of C5-C10hydrocarbons in the sample can provide information about the entirevolume of petroleum in a formation, once the presence of petroleum isestablished by identifying target substances that indicate the presenceof petroleum-associated organic acids (e.g., formic acid and/or carbonicacid, or only carbonic acid). Where samples sealed at the well or othercollection site are analyzed in the method of the invention, hydrocarbondata can directly correspond to the presence of oil in the associatedformation. In the case of old, non-sealed samples, hydrocarbons arelikely to be associated with fluid inclusions only, and the presence ofhydrocarbons alone in such materials may not be sufficient to accuratelyidentify the presence of petroleum in the formation in question.

In one aspect, the analytical method comprises analyzing the amount ofwater in the analyzed gasses (e.g., the trap-released gas in a method inwhich gasses are trapped and released). I have surprisingly discoveredthat high water concentration (in geologic material and/or in a sampleof such material) can be indicator of oil saturation. While not wishingto be bound by any particular theory, I believe that one or more organicacids, such as carbonic acid, formic acid, and/or acetic acid, whichis/are present in cuttings or samples will break down in the performanceof certain aspects of the inventive method thereby generating more waterthan would ordinarily be present in the sample (e.g., from analysis ofsuch cuttings by extraction of gas therefrom containing volatilecompounds, capturing such gasses on a liquid nitrogen trap, releasingsuch gasses from the liquid nitrogen trap in a predictable manner, suchas through accelerated warming of the liquid nitrogen trap, andsubjecting the released gasses to mass spectrometry analysis). However,in other aspects of the invention, other compounds than water are alsoor alternatively analyzed to assess the sample. This is particularlytrue as other organic acids associated with samples may not releasewater.

In one aspect of the invention, detection of excess water associatedwith a sample as an indication of petroleum-associated hydrocarbons ismade under conditions in which petroleum compound-associated excesswater in the sample can be detected and distinguished from other waterin the environment. For example, in aspects of the invention in which aliquid nitrogen trap is used in the method and/or incorporated into thedevice/system of the invention, the observation of water at temperaturesbelow that which normal water release is expected. Thus, for example, inone aspect the method comprises the detection of water at a temperaturethat is significantly colder than −55 degrees C. (a temperaturerepresenting about the lowest temperature at which water would typicallybe expected to be released and detected), such as a temperature of about−70 degrees C. or less (colder), about −80 degrees C. or less, about−100 degrees C. or less, about −110 degrees C. or less, about −120degrees C. or less, or even cold temperatures, such as about −130degrees C. or even about −140 degrees C. (e.g., about −100 degrees C. toabout −200 degrees C., such as about −120 degrees C. to about −180degrees C.). In experiments conducted with systems of the invention,such as the system exemplified in FIG. 1, water can be detected whenreleased at temperatures of about −140 degrees C. (a temperaturenormally associated with a carbon dioxide peak/release) and at highertemperatures (present in the system when the system is allowed to warmor is warmed by the application of heat from heaters in or on thesystem), but above −55 degrees C. Typically, the detection of water by amass spectrometry system will occur in a plurality of distinct peaksassociated with such temperature increases, ranging from about −140degrees C. to about −55 degrees C. in such a system/device. Withoutbeing bound by theory, it is believed that the detection of water undersuch abnormally cold conditions reflects the breakdown of organic acidcompounds during or after release from the trap and/or from watergenerated by acid decomposition by ion fragmentation resulting fromelectron bombardment under high vacuum in the mass spectrometer. In anyevent, the detection of water under such cold conditions, especiallywhen combined with conditions that would lead to and/or permit thedecomposition of organic acids associated with samples, such aspetroleum well-associated cuttings, is another important aspect of theinvention.

In particular aspects, if the water evolution (generation) caused byacid decomposition occurs during, or after, acid release from the liquidnitrogen trap then some of the water, but typically less than all of thewater, created by acid decomposition may be re-trapped on the LN2 trap,but the remainder of that newly formed water escapes the trap and isanalyzed. Other noncondensable gasses that form from the acids'decompositions, e.g., methane from acetic acid and carbon monoxide fromformic acid, typically are not trapped back onto the trap, but areusually transported and analyzed in the mass spectrometer upon theacid's evolution from the trap.

The separation of water evolved from acid breakdown from normal watervia evolution from a trap, for example a cryogenic trap such as a liquidnitrogen trap, has not been previously described by others, and thisphenomenon is a unique advantage of this invention. As discussed hereinmapping of oil and gas associated acids using water and other indicatorcompounds is a unique feature of this invention and has manyapplications for oil and gas exploration and production.

In yet another aspect, the method comprises a P₂O₅-based analysis of thewater content of one or more samples analyzed in the method. Gas from asample (typically after heating to drive water off the rock beforerelease of the gas) can be transferred around/over a P₂O₅-containingapparatus or container (with a known weight) and the weight thereaftermeasured to determine the amount of water present in the sample. Suchmethods can be advantageously performed on water in fluid inclusions aspart of the inventive method, as water can be difficult to analyze inthe context of analyzing fluid inclusions.

In one aspect, the method includes using hydrocarbon-containing fluidinclusions as a negative indicator of the presence of oil. In certainaspects the presence of hydrocarbon-containing fluid inclusions is anegative indicator of the presence of oil in a material and the presenceof a low number of hydrocarbon-containing fluid inclusions, particularlyimmediately adjacent, usually overlying, a zone of abundant oil and gasfluid inclusions, is typically indicative of a high chance of oil in thematerial. Such analysis can be included as part of the inventive methodsdescribed herein, and, in and of itself, represents an aspect of theinvention. Thus, for example, the invention provides a method of oil payzone mapping by solely or in combination with other methods examiningthe number of hydrocarbon-containing fluid inclusions in a material andidentifying areas where the number of petroleum-relevant hydrocarbonfluid inclusions are relatively low (less than about 10% of the number,e.g., less than about 5% of the number, of fluid inclusions inwater-associated areas, such as a water leg) or not detectable as areashaving a high likelihood of representing oil pay zones. Of course, thisis not true for the pore fluids (present day fluids present at thesite), which can be analyzed by the other aspects of the invention.

In another aspect of the invention the method comprises the step ofanalyzing released gasses for carbon dioxide. Carbon dioxide, likewater, can be produced from the breakdown of organic acids contained inthe sample. In other aspects, this step is avoided, as may also oralternatively be the case with respect to analyzing for the generationof water. This is because either substance, and particularly carbondioxide, can be confused with other sources of the substance, which maymake the analysis more difficult. Nonetheless, in certain instances theanalysis of carbon dioxide in the analyzed gasses, is an aspect of theinvention.

In another respect, methods of the invention can comprise analyzing theanalyzed gasses for the presence of carbon monoxide, which can beindicative of formic acid being present in the sample (and, thus, usefulin mapping of oil pay zones). Carbon monoxide can be detected usingconventional carbon monoxide detection devices, which are commerciallyavailable, or by using technology similar to that which is employed insuch devices. The carbon monoxide detection can be used to identify payzones within a well, where areas of a well associated with a relativelyhigh amount of carbon monoxide indicate the presence of petroleum insuch an area (e.g., at a certain depth of a well). Within a well, thepresence of about 35% or more, such as about 50% or more of the maximumdetected amount of carbon monoxide (which can be set as 100%) istypically indicative of a petroleum-relevant amount of carbonic acidand/or formic acid, typically formic acid, at such site (in some cases,the method is focused on the identification of the presence of carbonicand/or formic acid, typically formic acid, which will be indicative ofthe presence of oil in the sample and related material).

In another facet, the invention provides methods for determining thepermeability of a formation or composition. Such methods typicallyrequire a multiple aliquot method applied to samples under differentconditions, such as different pressures, so as to assess thepermeability of the sample (and, correspondingly, the formation).

Such methods are typically performed with samples primarily or entirelycontaining non-fluid inclusion volatile substances. In other aspects,the methods are performed in materials comprising fluid inclusions.

A sample can be, for example, subjected to different pressures torelease different aliquots, and each respective aliquot analyzed for onemore substances, such as hexane (or methane, propane, pentane, etc.).The relative amounts of the target material released under bothconditions is analyzed with the output of the analysis being indicativeof the permeability of the sample (and thus the formation). The analysisof such methods can at first appear counter-intuitive, this is becausemany samples, such as cuttings, can either be highly permeable,relatively impermeable, or contain zones of both high and lowpermeability. For example, with respect to hexane, if the application ofa first and relatively weaker vacuum results in a relatively largeamount of hexane being released from the sample and analyzed (comparedto the second aliquot performed under a stronger vacuum), this resultwill typically be indicative of low permeability of the sample. Thissurprising outcome is because most of the petroleum-related hydrocarbonsthat could be lost in the first aliquot in such material will be lostbetween the generation of the sample (e.g., the drilling that producedthe cutting) and the analysis of the sample for high permeabilitysamples. Therefore, if a greater amount of hexane or other relevanttarget substance is released and analyzed when the first vacuumcondition is applied such a result indicates that the permeability ofthe sample is relatively low, because the hexane was not lost betweengeneration of the sample and analysis. If the sample has relativelygreater permeability it typically will release more hexane on theapplication of a strong vacuum, because only the material in the samplewith low permeability will release hexane at such time. Thus, theproportion of hexane or other target substance released from a firstaliquot and a second aliquot by methods of the invention can be comparedto provide an indication of permeability of the sample is another aspectof the invention. The other gases analyzed besides hexanes can also beused in evaluating permeability. In fact, it can be useful to study therelative permeabilities of the various volatile constituents of thesample.

In other aspects, permeability can be assessed by infusing the samplewith a substance, such as noble gas, and then measuring the release ofthat infused substance, alone or in combination with the release ofendogenous volatile substances, such as hexane.

In one aspect, the invention provides a method of determiningpermeability of a material by comparing the release of one or morevolatile substances and/or classes of volatile substances from the samesample from the material under two or more different conditions thatpromote the release of volatile substances from the sample, such asapplying two different pressures to a single sample. In some aspects,this process is applied to a plurality of samples, such as at least 10,at least 20, at least 50, at least 100, at least 250, at least 500, oreven at least 1,000 samples. In some facets, at least three conditions,at least four conditions, at least five conditions, or more are appliedto a single sample to aid in the assessment of permeability.

In one example of the permeability evaluation method described above, afirst aliquot is extracted from a sample, such as a cutting from an oilwell, at a pressure of about 50 millibars. A second aliquot can then beextracted from the same sample at a pressure of about 5 millibars.Permeability can then be estimated by comparing the data obtained fromthese two analyses. In other words, the force required to extractvolatiles out of a sample can aid in the determination of permeability.This is of further significance in that conventional permeabilitymeasurements cannot be performed on cuttings samples, but, rather, aretypically applied on conventional core or rotary side wall core samplesand are based on the pressure required to push a fluid through auniformly shaped piece of rock, usually a cylinder. Typical fluids usedin conventional permeability measurements include helium and mercury.Such permeability measurements cannot be applied to well cuttings asthey require a coherent volume of intact rock.

A formula that can be useful in estimating the permeability usinghexanes in accordance with the above-described aspects of the inventionis:100*(hexanes^(aliquot 2)−hexanes^(aliquot 1))/(hexanes^(aliquot 2)+hexanes^(aliquot 1))In one aspect, this formula is used in the determination ofpermeability. Values obtained from this expression range from 100 to−100. A value of 100 indicates hexanes were only obtained from aliquot 2in a 2-aliquot analysis with no hexanes analyzed in aliquot 1, these arethe most permeable samples. A value of −100 indicates hexanes were onlyobtained from aliquot 1 with no hexanes analyzed in aliquot 2, these arethe least permeable or the tightest samples.

The nature of the calculation reflects an unexpected aspect of theinvention. Ordinarily it would be expected that the most permeablesamples will have high hexanes on aliquot 1 and low hexanes on aliquot2. This however is not the case. I have surprisingly discovered that inthe most permeable samples the most easily removed hexanes are lostbetween the time the rock is disrupted by the drill bit and its rise tothe surface suspended in the drilling mud, until the sample is sealed ina brass tube either at the well site, or at some later time. Hence, themost permeable samples show the least amount of hexanes from aliquot 1and the most amount of hexanes from aliquot 2, in the type of methoddescried here. Thus, a sample that shows high hexanes on aliquot 1 andlow hexanes on aliquot 2 is a sample with very low permeability suchthat hexanes are not predominantly lost from the sample by drill bitdisaggregation and transport to the surface in the drilling mud atresidence time under atmospheric conditions before being sealed in acontainer, such as a brass sample tube, and analyzed.

Permeability in samples analyzed according to these aspects of theinvention can vary as a function of compound size, shape, mass, andchemical affinities. It is therefore instructive to consider a range ofpermeabilities using several of the compounds that are analyzed, or allof the compounds that are analyzed. Hexanes can be a preferred measureof permeability for the method (or inclusion in the method) becauseunder natural conditions prior to analyses the hexanes should beliquids. And under all analytical conditions used in our analyses thehexanes should be gaseous. This then removes any possibility withconfusing boiling for permeability.

As mentioned elsewhere herein, in some aspects, the method of theinvention comprises analyzing the presence of hydrocarbons. In somecases, the method comprises the analysis of short hydrocarbon chainmolecules. In other aspects, the method comprises analyzing both longchain and short chain hydrocarbon molecules. For example, C2-C15hydrocarbons, such as C2-C12 hydrocarbons, e.g., C2-C10 hydrocarbons canbe trapped and analyzed using a cryogenic trap method, and methane canbe collected and analyzed using NCG methods described elsewhere herein.

The analysis of long chain hydrocarbons is another facet of theinvention which distinguishes it from prior art methods which aretypically performed very quickly and, thus, are incapable of analyzingsuch materials effectively, in that such methods do not sufficientlycause longer chain hydrocarbons to be released from samples. Where alonger period of time is used to trap materials, such as where acryogenic trap/pump is employed for about 10 minutes or longer, such asabout 12 minutes or longer, or about 15 minutes or longer, relativelylonger chain hydrocarbons can be capture and then analyzed by themethod, which is another distinguishing characteristic of such methodsfrom the prior art. Relatively longer chain hydrocarbons meanshydrocarbons comprising a backbone of six or more carbon atoms, such asseven or more carbon atoms or eight or more carbon atoms.

In a further aspect, the invention comprises consideration of pressurechanges in the performance of the method. Methods of the invention cancomprise the breakdown of compounds, such as organic acids (e.g., formicacid, carbonic acid, or acetic acid) to other compounds (e.g., carbonmonoxide and water in the case of, e.g., carbonic acid, or methane andcarbon dioxide in the case of, e.g., acetic acid), which can result inchanges (typically increases) in pressure in the system because of thegeneration of such non-condensable gasses (carbon monoxide and methane).

In still a further facet of the invention, methods in which changes inmoisture are performed on samples are provided, particularly after suchsamples are subject to conditions in which organic acids, such as formicacid or carbonic acid, can be formed, particularly from materialspresent in the sample. For example, in one aspect the method comprisesubjecting samples to conditions that can form carbonic acid, which maybe associated with and/or may further be broken down under suchconditions or other conditions achieved in the performance of the methodto form water, wherein the presence of such generated water isindicative of the carbonic acid or formation of the carbonic acid, andthereby indicative of the presence of oil-related hydrocarbons in thesample (and the material). For example, subjecting oil well cuttings tomethods described herein wherein gas is released from the cutting, suchas under varying degrees of vacuum pressure, trapped by a liquidnitrogen trap or a similar device, and released from such a trap to massspectrometry analysis, water can be formed, and such water can bedetected by any type of conventional method, including humidity ormoisture detection techniques that are known in the art. The detectionof water can, in some contexts, provide an indication that oil-relatedhydrocarbons are present in the sample and material and thus the methodcan comprise running an analysis for changes in moisture, humidity, orotherwise detecting changes in water content, following application ofsuch methods or forces on the sample.

In another aspect, the invention comprises analyzing the effects ofpressure in the formation by examining the sample for the effects offormation pressures. In such aspects, typically a number of samples fromdifferent areas or depths are obtained and examined for changes in fluidcomposition, which can be indicative of a discrete/large change inhydrostatic pressure between the different areas of the formation (e.g.,from a zone of unusually high pressure to normal pressure or from a zoneof normal pressure to a zone of unusually low pressure), which can berelevant to how materials in the formation will behave under differentconditions.

Any of the analytical methods described herein that can be applied toanalyzed gasses in the methods of the invention can be, and often are,combined, to provide a more complete analysis. For example, in oneaspect the method includes the step of analyzing the analyzed gas forthe presence of carbon monoxide, increased water content, and/orpresence of C5-C10 hydrocarbons. In another exemplary aspect, the methodcomprises analyzing the analyzed gas for the presence of carbon monoxideand carbon dioxide.

The methods described above can be practiced with or without theapplication of other methods used for the identification, assessment,and/or characterization of formations and/or materials therein, such asthe petroleum content of a formation. For example, in one facet of theinvention, the inventive methods described herein are applied withoutperforming conventional fluid inclusion analysis or gas chromatographicanalysis of the material or sample. However, in another dimension, themethods of the invention can be performed in combination with such otherconventional analytical methods, so as to potentially enrich theinformation gathered about the material. Another method that can becombined with these methods is to examine samples for fluorescence datawhich can provide evidence of oil staining of the sample.

In one exemplary aspect, the invention comprises combining informationgathered from the primary methods described herein with informationgathered from fluid inclusion analysis. Methods of performing fluidinclusion analysis are described in my previous patents referenced anddescribed elsewhere herein. In one aspect that may be particularlyadvantageous in certain contexts, the method comprises performing afluid inclusion analysis that comprises analyzing fluidinclusion-trapped oxygen, nitrogen, or the combination thereof, whichare associated with the material. These non-condensable gasses canprovide information about the paleontological (paleo-exposure) surfaceof the material, which may assist with, for example, oil exploration.

In still another aspect, the methods are practiced in combination withgamma ray mapping for, e.g., identification of types of geologicformation, e.g., identification of sands vs. shales. Including gamma raymapping as a component of the analytical method can determine the natureof the formation material (sand vs. shale). The size of a formation canbe relevant to assessing whether the deposit of the material (e.g., oil)is of sufficient amount to be economically advantageous for producingthe material (again, typically oil) from the formation.

In another, more general sense, the invention provides methods ofanalyzing the content, such as the organic acid content and/or watercontent, of cuttings that were intimately associated with drilling muds,for example, to perform oil pay zone mapping. In fact, generation of oilpay zone mapping is a preferred and particularly advantageousapplication of this and other methods of the invention. Most cuttingsfrom oil well sites will be intimately associated with drilling muds (anexception is an air drilled cutting). I have discovered that suchcuttings can provide a unique opportunity for analysis of drillingareas. While not intending to be bound by any particular theory, Ibelieve that the interface between such cuttings and drilling muds willform physiochemical structures that retain organic acid contents andpossibly other contents, due to the normal differences in pH of therespective materials (mud and cuttings). Accordingly, methods ofpetroleum analysis, and pay zone mapping, comprising preferentiallyusing such materials, is an important aspect of my invention. Themethods that can be used to analyze the organic acid content of suchcuttings can be any of the methods that are described herein or thatotherwise are known in the art. What characterizes the methods of thisparticular aspect of the invention is that the method, at least in part,focuses on cuttings that have had such intimate interactions, therebylikely forming such unique conditions for maintaining their organic acidcontent. Again, the application of methods of this invention todetermine the organic acid of such cuttings is particularly useful inpay zone mapping. This is because such organic acids are typically incuttings that are co-located with petroleum in many geologicalformations.

One of the advantageous aspects of the inventive methods describedherein is the application of the invention (such as the analysis oforganic acid content) using samples obtained from fresh waterenvironments (environments in which the water associated with most,substantially all, or all of the samples analyzed contains relativelylittle or no salt). For example, in certain aspects the method isperformed with water having a saline content of less than about 10,000ppm, such as less than about 5,000 ppm, such as less than about 2500ppm. In this respect, the organic acid content analysis methods of theinvention can work under conditions where conventional well loggingmethods fail, due to the nature of the fresh (low saline) water presentat such sites.

In still another aspect of the invention, mud-associated cuttings haveretained or captured water/brine from the site at which the cuttings aregenerated, and the method comprises analyzing the water/brine associatedwith such mud-associated cuttings, for example by analyzing theconductivity of such water/brine. Again, most cuttings will be mudassociated when taken from petroleum drilling sites.

These amounts of water/brine are typically small and the method maycomprise freezing such micro-amounts of water and then subjecting themto a suitable method for analysis, such as scanning electron microscopywith energy dispersive x-ray fluorescence, electron microprobe, and/oran ion probe, or other suitable method, to analyze the water/brinecomposition of the water in such cuttings. Such data can be used bypetrophysicists to evaluate the oil and water saturation of a well ascurrently determined by conventional well logging methods. This andother such information that is obtained from such mud-associatedcuttings can be used to map the presence of oil or other substances fromsuch samples, and, thus, can be used as another method to perform “payzone mapping”, in accordance with the invention. In one aspect, themethod comprises only analyzing such brine/water content. These methodscan be particularly important in that resistivity (which today issuccessfully based on the presence of brine in a material) currently iscommonly used as a key quantifier of petroleum content of drilling sitesand other geological formations.

The methods of the invention that involve the analysis of volatilesubstances can be performed with any suitable number of aliquots takenfrom any suitable number of samples. In some cases, it can beadvantageous to take a single aliquot from each sample in a set ofsamples. Thus, the invention provides a method in which a suitablesample is provided, the sample is subjected or exposed to forces thatcause release of a gas containing an analyzable amount of one or morevolatile substances, and the method includes the step of capturing(e.g., trapping and concentrating) a first trappable gas (such as acondensable gas in a system that relies on condensation of the gas) inor with a media or other means in an analyzable amount to generate analiquot, optionally but typically isolating the sample from the aliquot,and optionally but typically releasing at least an analyzable amount ofthe volatile substances from the trap or collecting means, andthereafter analyzing at least one aspect of the chemistry of the one ormore released volatile substances. Often it will be the case that the“single aliquot” will actually comprise a condensable gas component(sub-aliquot) that is trapped with a first trap and a non-condensablegas component (sub-aliquot) that typically is separately collectedand/or separately analyzed from the condensable gas sub-aliquot.

The forces applied or to which the sample are exposed can be anysuitable forces, such as those described above. In one set of facets,the method comprises subjecting the sample to a pressure of at least 1millibar and less than 1 atmosphere, such as between at least 1 millibarto about 100 millibars. The sample can be exposed to such forces for anysuitable amount of time. Particularly unique aspects of the inventioncomprise applying a gentle vacuum pressure, such as between about 1millibar and about 500 millibars, such as about 1-300 millibars, about1-250 millibars, about 1-200 millibars or about 2-200, 2-150, 2-100,3-200, 3-250, 3-100, 5-250, 5-200, 5-100, 1-50, 2-50, 3-50, or 5-50millibars of pressure for a period of less than 15 minutes, such as lessthan 10 minutes, such as less than about 9 minutes, less than about 8.5minutes, less than about 8 minutes, less than about 7 minutes, less thanabout 5 minutes, or even less than about 3 minutes, less than about 2minutes, or less than about 1.5 minutes or less than about 1 minute,such as about 0.25-15 minutes, about 0.33-12 minutes, about 0.5-12minutes, about 0.33-10 minutes, about 0.33-11 minutes, about 0.5-11minutes, about 0.5-10 minutes, about 0.65-about 11 minutes, about0.65-10 minutes, about 0.5-7.5 minutes, about 0.33-7 minutes, about0.5-5 minutes, about 0.33-5 minutes, about 0.75-7.5 minutes, about0.75-5 minutes, or about 1-10 minutes, such as about 1.5-9.5 minutes,such as about 2-9 minutes, such as about 4-8.5 minutes, such as about5-8.5 minutes, or such as about 6-8.5 minutes. The sample also oralternatively can be exposed to other forces comprises, such assubjecting the sample to a crushing force, optionally in addition to oneor more other forces such as vacuum pressure, vibrational energy, orradiation energy, such as laser excitation, or a combination of any orall thereof. Application of crushing forces can provide a frackabilityaspect to the method, in which measures such as ductility and/orhardness are determined (e.g., by crushing a flexible containercomprising the sample) as described above. The volatile substances canbe analyzed by any suitable means, typically by means that comprise massspectrometric analysis. In some aspects, the method can compriseremoving potentially interfering gasses from the media, but in otheraspects such a step is not practiced or is not necessary. In some casesthese methods are characterized by not heating samples to temperaturesof greater than 100° C. in performance of the method. In some aspects,the method comprises collecting and sealing samples at the wells versusloaded in lab samples. Such methods can comprise collecting andanalyzing samples in close proximity to the well site. For example, themethod can comprise performing the method within 200 feet, such aswithin 100 ft, 75 ft, or even 50 ft of where the samples are deliveredto the surface. The method may comprise transfer of the samples byconveyor, pneumatic tube system, or other system to a site, or evendelivery by drone, to a laboratory for analysis, which may be situatedwithin 0.5 miles, such as within 0.25 miles or even 0.1 miles of thewell site.

In another aspect, these methods are performed in relation to an activewell, such as a well that is under active drilling, such that the methodcan provide real-time or near real-time analysis of samples. Forexample, in some aspects the difference or lag time between the site ofdrilling (location of the drill bit) and the location of the samples inwhich the most recent analysis is performed is than about 50 feet, suchas less than about 40 feet, less than about 30 feet, less than about 20feet, or less than about 10 feet, 7 feet, 5 feet, or even less thanabout 1 foot. Such methods may comprise actually collecting samples inthe well line and, e.g., transmitting the data connected with thehardness of the samples, such as by crushing or squeezing in-wellcollected samples, to the surface through fiber optics, well linevibrational signaling, or the like. In other cases, the analysis ofsamples at the surface of the well can still provide an inexpensivealternative and/or complement to gamma ray mapping which is currentlyperformed and a faster analysis than x-ray diffraction methods currentlyperformed and can still be used as a means of mapping a material(formation, region), and directing drilling/fracking operations. Datacollected from such operations can be digitized or otherwise relayed asdata through a computer system and then used to automatically direct orprovide information to human operators through, for example, a graphicaluser interface, which can aid in the direction of well site operations.In some aspects, the method is performed with a well that has increasedmud flow as the compared with current rates of mud flow so as to provideimproved real-time analysis through cuttings, which may be particularlyuseful when the real-time cuttings analysis is performed with cuttingsdelivered to the surface.

The data collected in the analysis can be any suitable kind of data,but, as described herein, will favorably often include analysis ofacetic acid, formic acid, and/or oil saturated water associated with thesample. The analysis also or alternatively can include measuring theamount of methane, carbon dioxide, and/or carbon monoxide that isreleased from the samples or released from a volatile compound trap.

Given the variable nature of materials to be analyzed the scale of thedata that is analyzed in methods that are related to volatile compoundsanalysis can vary. This can be true even for a particularly kind of dataas the conditions in which the sample are collected can vary. Forexample, with respect to cuttings the age of the cutting, condition ofthe cutting and its storage, and the nature of the materials containedin the cutting can influence the scale. Thus, in one aspect the methodcan comprise evaluating the material either through routineexperimentation or by guidance provided through standards or similarmeans, such as machine calibration that is programmed based on thevariables (e.g., known oil wells of a similar nature can be mapped andused as a calibration for similar wells), to assess the right scale ofmeasurement for plotting or otherwise analyzing the data, as exemplifiedin the Examples provided below. The method typically then comprisesseeking indication of the presence or absence of one or more of thecompounds of interest. Where multiple samples from multiple locationsare taken typically a map or plot will be generated, again asexemplified in the Examples. In such a case the method will typicallycomprise manually or automatically seeking patterns in the data at theselected scale(s) that will indicate changes or anomalies or “hits”. Insome cases, the change in the amount of a target substance in a scalewill be from a “0” or near 0 level, or lack of detection, to thedetection of any value above 0. As another example, for example, whereoil as a percent of total rock value is used as a measurement, in somecontexts (e.g., rocks with a porosity of about 8%) a measurement of atleast 2% would be considered “high” oil value, and low values could beset at 0.1% or lower. By plotting the data clear patterns can be seen.Often times, a measurement of about 15% of the scale or more (e.g.,about 25%, about 30%, about 40%, about 50% or more), would be considereda “hit”. The analytical aspect of a volatiles facet of the inventionalso can comprise analysis of two or more types of data, such aspermeability at one depth and non-permeability at another, e.g., toidentify trapped zones of oil that can be very beneficial. Also oralternatively, various measurements, such as oil saturated water can becombined with other measurements such as formic acid, acetic acid andthe like, such that one can measure the petroleum pay zone andformations around the pay zone that are in fluid communication with thepay as evidenced by formic acid, acetic acid, and oil saturated water.The combination of permeability and other information, especially whencombined with other data from conventional means, can provide maps thatidentify one or more pay zones in a material/region. Use of dataincluding other hydrocarbons can further explain the nature of the oil,such as whether there is heavier or lighter oil present (or otherwisewhether the oil and/or gas deposits are of a similar or different natureand/or whether gas can be relied on to aid in the transport of oil tothe surface, etc.), and relative petroleum deposit locations, whetherthere is a “seal” (low permeability region) around the oil deposit,and/or oil deposit locations in relationship to water and other pocketsof oil and/or water in the material/region. Such data can aid indetermining whether or not different pay zones can be obtained togetheror separately and under what conditions pay zones can be obtained. Thus,for example, analysis of such data can reveal whether or not an oil orgas deposit is compartmentalized with respect to other deposits of oilin the material/region.

As stated above, the various disclosures relating to the methods of theinvention can be readily applied to devices and systems of theinvention, which are also exemplified in the examples provided below.Thus, in another facet, the invention provides devices that comprise (a)a container or chamber for receiving and isolating samples of a materialand (b) a detection component capable of detecting the amount of one ormore target volatile substances released from the sample, wherein thesubstance comprises carbon monoxide, acetic acid, formic acid, or acombination thereof, optionally in combination with hydrocarbons,inorganic gasses, or a combination thereof. In still another facet, theinvention provides a device comprising a crushable component or materialthat can contain samples, which when crushed provides informationconcerning the strength of the sample (and thus the material) and asystem that comprises such a device and means for crushing the device(as well as optionally means for measuring the information, storing theinformation, relating the information, etc.). In still another facet,the invention provides devices and systems that are capable of bothanalyses.

With respect to devices that are capable of volatile substance analysis,a device of the invention typically comprises an energy input componentthat promotes the release of volatile substances from the sample. Theenergy input component typically is or comprises (a) a pressuregenerating device or system, (b) a device or system that promotesrelease of volatile substances through mechanical forces, thermalforces, or both, or a combination of (a) and (b). Often the device orsystem will comprise means (component, system, or the like) forisolating volatile substances released from the sample from the sample,the environment, and/or other components of the system or device, suchas one or more operable valves. Devices and systems often will include atrap, which may be a non-selective or a selective trap, or comprise bothkinds of traps. The trap can be, for example, a liquid nitrogen trap,which is capable of capturing volatile, condensable gasses, releasedfrom samples, such as cuttings. The dimensions of such devices aredescribed elsewhere herein, as are suitable materials from which suchdevices can be made.

Devices for volatile compound analysis typically include means formeasuring the volatile substances. This can include, e.g., a carbonmonoxide detector or other kind of chemical detector and also oralternatively a less specific detection system, such as a massspectrometer, examples of which are provided elsewhere herein. Whereadvantageous, the analytical parts of the system may be optionallyisolatable from other parts of the system, such as to ensure properoperation and/or to avoid false signal events. The device/system of theinvention may further comprise a programmable or data logic componentfor collecting data, relaying data, storing data, and the like, whichmay include alarms, automatic device means (such as means forcontrolling directionality of a drill), and/or a graphical userinterface. The operation of the components of the device/system cansimilarly be automated and/or placed under control of a programmableunit or computer system.

In another aspect, the invention provides systems or devices forchemical analyses of volatile compounds in a sample of a material thatcomprises (a) a cryogenic trap that can be cooled and held attemperatures that are capable of capturing target volatile substanceswhen such substances are in fluid communication with the trap (e.g.,temperatures of about −100 degrees C. or colder, such about −110, about−120, about −130 degrees C. or less) (e.g., the device/system willtypically include a cooling component or cooling means that is capableof selectively cooling the cryogenic trap, which can be in practice one,two, or more separate traps); (b) optionally, but typically, a componentor system for selectively warming the cryogenic trap in a controllablemanner, (c) one or more devices or systems for applying one or moreforces to samples that the system is applied to, such as a vacuumsystem, preferably with the ability to apply multiple levels of vacuumpressure to the sample, and in preferred aspects the ability to applyrelatively low/gentle vacuum on a sample, such as about 25-150 millibarsof pressure (e.g., about 60-120 millibars of pressure) to a sample, (d)components for containing the volatile substances and keeping thesubstances isolated from the environment, such as a housing, (e)components for selectively isolating the trap from the sample, such thatvolatile compounds can be exposed to the trap only after cooling to adesired temperature, (f) an optional component for the capture ofvolatile substances that will not condense on the trap, which typicallyis selectively isolated from the other substances such that thenoncondensable materials can be separately analyzed from the materialsthat condense on or otherwise bind to the trap and are thereafterreleased from the trap, and (g) a device for analyzing at least some ofthe volatile substances released from the trap, such as a massspectrometry device, optionally with means/components for selectivelyallowing access of the volatile substances to the analytical device(e.g., one or more selectively openable valves), and (h) means orcomponents for causing the transport of at least some of the volatilesubstances captured in the enclosed system. Such a system may also oralternatively further comprise (i) a component or means for evacuatingany noncondensable gases out of the cryogenic trap as and if necessarywithout release of any condensable volatiles from the cryogenic trap ifthe analytical method requires high vacuum, such as a selectivelyoperable pumping system. Systems that have means/components for analysisof non-condensable gasses/materials may further comprise means forcapturing a set volume of such non-condensable materials, such asselectively operable vacuums that can act on such materials and/orcomponents/means for selectively exposing such materials to theanalytical part of the system and often means/components fortransporting such materials to the analytical componentry of thesystem/device.

As described above, a cryogenic trap can be generated by contacting asuitable medium with a cryogenic substance such as liquid nitrogen,liquid argon, liquid oxygen, liquid air, liquid helium, dry ice, a dryice slurry, normal ice, a normal ice slurry of water ice in fresh water,a normal ice slurry of water ice in a saline brine, or any othernaturally cooling substance capable of achieving the minimum temperaturerequired to freeze the substance(s) of interest onto the cryogenic trap.A cryogenic state may also or alternatively be achieved with mechanicalrefrigeration or cooling as may be achieved with a Kelvinator device.The Kelvinator or other cryogenic device must be able to achieve theminimum temperature required to freeze the substance(s) of interest ontothe cryogenic trap.

A cryogenic trap component can have any suitable configuration. In oneexemplary embodiment, the trap will be configured such that cooling ofthe cryogenic trapping device occurs on the exterior of a cryogenicchamber and volatile substances adhere to the interior of the cryogenicchamber. Alternatively, a trap can be provided wherein cooling of thecryogenic device occurs on the interior of the cryogenic chamber andvolatile substances adhere to the exterior of the cryogenic chamber.

In one aspect, the cryogenic trap comprises one or more materials thatare suitable for cyrogenic trapping, which typically are selected frommaterials that comprise one or more suitable metals, such as aluminum,copper, gold, silver, platinum, palladium, stainless steel, brass,bronze, nickel, cobalt, or any other appropriate metal, including alloysand/or any suitable combinations of such materials. A trap also oralternatively can be composed of a non-metallic material, optionally anon-metallic material that forms a substrate for trapping of volatilesubstances, such as, for example, carbon fibers, peek, natural orindustrial diamonds or diamond films, glass, ceramics, or any otherappropriate non-metallic substance or combination of such substances,alone or in further combination with one or more metallic substances.The trap can have any appropriate shape or configuration, including, forexample, a shape selected from cylindrical, a u-tube, polygonal,sphereical, funnel shaped, ribbed, helical, and/or botryoidal shape, orany other appropriate shape.

A system or device comprising a cryogenic component or system accordingto such aspects of the invention can be configured to analyze any typeof volatile compounds or volatile compound-associated sample(s). Whilethe description herein places significant focus on extracting volatilesubstances from geologic materials, especially from materials from oiland gas wells, and particularly from cuttings from oil and gas wells,the methods of the invention can be performed, as stated already herein,with other types of samples and in another facet of the invention mayeven be practiced with volatile fluids that are independent of any kindof solid sample. For example, in one aspect one or more volatileanalysis methods of the invention, such as those described above, isalso or alternatively applied to a liquid, such as one or more drillingmuds. In another aspect, such a method or set of methods is also oralternatively applied to a gaseous substance (e.g., a substance that issubstantially, predominately, or entirely in a gaseous state undernormal atmospheric conditions). In such aspects of the invention theinventive method can comprise filling a container or a component of thesystem with the gas to be analyzed and allowing the gas to make contactwith a trap, such as a liquid nitrogen trap, and then subjectingtrap-released gasses to analysis, such as by mass spectrometry. Wherethe gas is provided in a container, such as a vial, the method caninclude the step of filling the vial, optionally sealing the vial, andoptionally forming a fluid flow in a sealed manner between the vial andthe system such that volatile substances in the gas are not lost eitherdue to escape or reaction. Alternatively, gas can be captured in adevice, such as a syringe, and introduced into a system, e.g., a systemunder vacuum, by passage of a needle through a septum, and therebyemptying some, most, all, or essentially all of the components of thesyringe into an inlet into the system and eventually, immediately, ornear immediately thereafter into an inlet to a trap and thereafter ananalytical device (or where a trap is not used, directly to ananalytical device according to such aspects of the invention). Yetanother alternative facet of the invention provides a method in which agas containing amounts of volatiles, such as very low/trace amounts ofvolatiles in the gas, is to permit condensation of the gaseous volatileson a trap, such as a liquid nitrogen trap, over a relatively longerperiod of time, to allow accumulation of even trace amounts of volatileson the trap. Such a process could be used to detect extremely smallamounts of explosive associated volatiles in air, or of trace amounts ofhydrocarbons and/or organic acids in air associated with petroleum seepsor other relevant trace chemicals such as environmental contaminants. Assuch, such an instrument, and even many of the other devices and systemsdescribed herein, may be useful deployed as a mobile unit in a car,truck, plane, boat, or even a rocket. A system with multiple liquidnitrogen traps would provide continuous monitoring as while one trap wasextracting a sample to analyze, another trap would be analyzing thepreviously trapped sample.

Systems and devices of the invention will typically comprise a device ora means for introducing volatiles from a sample into the system in anisolated manner. In one advantageous aspect, as exemplified elsewhereherein, the system includes componentry and/or means for introducingvolatile substances to the device/system by way of syringe or needleinjection, which often advantageously comprises a portion thatpunctures, pierces, or otherwise traverses a septum, which typicallywill be associated with a sample container in which the samples can becontained, preferably in a sealed state, such that loss of volatilesubstances is minimized (e.g., the system can comprise one or moresamples that are hermetically sealed to a cryogenic trap inlet). Thesystem will typically comprise componentry/means for generating flow ofgasses to the cryogenic trap, such as pumps and the like. The system mayfurther optionally comprise sources of gas, such as air or other gasses,which can aid the flow of volatile substances in the system/device.

An analytical device for the assessment of volatile compounds accordingto such aspects of the invention typically comprises a massspectrometer, but also or alternatively can comprise one or moreadditional analytical devices including, for example, a gaschromatograph; an infrared spectrometer; a Raman spectrometer; or anycombination of these including multiples of the same type device (e.g.,multiple mass spectrometers); or any other appropriate analytical meansand/or combination of analytical means. As described elsewhere thedevice/system will often include programmable logic means/componentsthat can put the operation of the device under automatic control andcapture, record, and/or transmit and/or display data obtained from theperformance of the method in digital form, print form, or in other knownforms.

The combination of the above-described components into devices andsystems provides several useful and novel additional or alternativeaspects of the invention. Thus, for example, the invention provides anovel and useful device that comprises (a) a cryogenic trapdevice/component that is in fluid communication, typically selectivefluid communication, with one or more mass spectrometers, usually in aconfiguration such that permits the release of material from thecryogenic device/component to the mass spectrometer component. Such adevice can comprise means/components for flow of material through thesystem and means/components for selectively heating the cryogenic trap.

In another aspect the invention provides devices and systems comprising(a) a non-selective trap that can capture volatile substances in sampleof materials, (b) a housing or other enclosure that prevents loss ofvolatile substances in materials in the system (at least to significantamounts, such as by maintaining at least 90%, at least 95%, at least98%, or even 99% o more of the volatile substances associated with thesample once the sample is placed in a secure manner in communicationwith the system), (c) an analytical device that can detect one or moreprimary and/or secondary compounds that are associated with targetmaterials, such as oil and/or natural gas, (d) components or means fortransporting volatile substances to the trap and (e) components or meansfor selectively releasing materials from the trap in a manner thatallows for determination of the presence or absence of at least one,preferably at least two, and typically 3, 4, 5, or more (e.g., at least6, at least 7, at least 8, or even 10 or more) substances from thesystem. Typically such a system will further comprise one or more forcesthat can be applied to the system for promotion of the release ofvolatile substances, such as different pressures, which may revealadditional information elements concerning the substances such aspermeability of the sample and/or will comprise means/components forcausing chemical reactions of the volatile substances, for example byproducing water in the system from one or more trapped substances. Thesystems can also include means/components for selectivelycrushing/squeezing the samples and providing a related measurementthereto such that compressibility and the related ductility/hardness ofthe sample can also or alternative be provided. The sample containersprovided by the invention are also novel and useful devices in and ofthemselves. Thus, for example, the invention provides a sample containercomprising a selectively puncturable section, a housing that is capableof containing sample materials, such as oil-well associated cuttings,and that also is at least substantially impervious to the release ofvolatile substances, and optionally a crushable selection or componentthat allows for the application of crushing/squeezing forces on thecontainer, in a known manner, resulting in a measurable amount ofcompression of the container that provides relative information aboutthe hardness/ductility of materials in the container and also optionallypromotes the release of volatile substances. Optionally and often such acontainer is configured to be in sealed fluid communication with one ofthe devices of the invention.

EXEMPLARY EMBODIMENTS & APPLICATIONS OF THE INVENTION

The following examples further illustrate various aspects of theinvention but should not be construed as in any way as limiting thescope of the claims or the rest of the disclosure provided herein.

Example 1

This example provides a description of an exemplary device/systemaccording to certain aspects of the invention and that also is suitablefor application of several of the inventive methods described herein. Anoverview of the exemplary device is provided in the following figure(FIG. 1).

With respect to the device/system shown above, #1 depicts a first samplecontainer, as described elsewhere herein. The first sample container #1contains the sample of the material, such as cuttings taken from an oilwell. The sample container #1 in the case of the depicted system issealed and made of an impermeable material. The top portion of anysample container used in the system, such as the first sample container#1, is penetrable by the needle #2, which provides a passageway andmeans for transferring gasses released from the sample into the rest ofthe system, either immediately after penetration and/or after generationthrough the application of one or more forces acting upon the sample.

A second sample container #2 and a third sample container #3 are alsoshown, reflecting the fact that systems of the invention often are runwith numerous samples in a given run or load (e.g., at least 5, at least10, at least 15, at least 20, at least 25, at least 30, at least 35, atleast 50, or more samples). In the case of the depicted system, a samplecarousel, #4 is provided, into which the several samples to be analyzedin the particular run are loaded. Other types of automation other than acarousel could also be used, such as a cartridge holding a plurality ofsamples in either a vertical or horizontal profile (not shown), or inany angle between vertical and horizontal, that can deliver samples inany position appropriate for volatiles analyses (also not shown). Thesamples loaded in a particular load or run typically are related to oneanother, such as samples taken from a particular well site andmaintained under particular conditions, but this is not necessarilyalways the case. In some embodiments of the invention, the carousel #4is automated to run once the analysis on a particular sample iscomplete, often this will be controlled by a programmable computer whichis connected to the system and in control over various functionsoperating in the system (and thus components of the system). Thus, forexample, when analysis has been completely performed on the first samplecontainer #1, the carousel can automatically rotate placing the secondsample container #3 into position, whereby a penetrable portion of thatsample container, can be penetrated, such as by the needle #8. Theloading and transferring need not be in the form of a circular carousel,but could be, for example, in the form of a conveyor, or any othersuitable sorting mechanism. The penetration of sample containers by theneedle can, also, be under automatic operation or, more typically, issubject to operation by robot or computer once certain conditions havebeen satisfied (and subject to manual override). The sample containersdepicted here comprise sidewalls that are made of a sturdy butcrushable/collapsible material, such as brass, of a relatively fixedthickness.

The depicted system also comprises a ram #5 which is made of a materialthat is suitably composed and configured such that it can deliver animpact on the crushable sidewall or other modifiable portion of thecontainer. For example, ram #5 may be made of a stronger metal, such assteel, which can repeatedly be used to crush the sidewall of thecontainer and thereby deliver a crushing force to any sample materialscontained therein, such as oil well cuttings. Ram #5 is typicallyconnected to pistons #6, which can be air pistons or another suitabletype of piston(s). Pistons #6 and ram #5 typically form a squeezing orcrushing apparatus or system together, as depicted. The pistons #6 canbe used to drive the ram #5 into the crushable portion of the samplecontainer, e.g., #1, either upon a user command, under some automaticcondition, and/or when directed by a computerized control system. Theram is typically driven by the piston or other driver mechanism (e.g., apowerful spring) into the container with a force that is suitable forcrushing a portion of the container and delivering enough force to crushthe sample material, thereby either releasing volatile compounds orassisting in the release of such volatile compounds in combination withthe application of other forces or energies, such as vacuum pressure.The system typically comprises an anvil, #7, which assists in thecrushing of the container, #1, by providing a hard surface against whichthe container is pressed when the ram #5 is brought into contact withthe container #1 by application of the pistons #6.

The needle #8 also is typically associated with a needle assembly, whichcomprises a connection block #9, which, as depicted, is connected to aleveling screw, #10, which can raise or lower the needle, so as to causethe needle #8 to puncture a seal or other puncturable portion of thecontainer #1 when engaged (alternative devices or means for raisingand/or lowering the needle also or alternatively could be used).Engagement can be performed manually, automatically, and/or bycomputerized program control. The connector block #9 comprises a channelportion that gas passing from the sample container #1 and through theneedle #8 can flow. In the depicted embodiment, the channel portion ofthe connector block #9 is in communication with a selectably engagable(closable/openable) right-angle valve #11, which controls the flow ofgasses from the sample container/needle/connector block into the otherportions of the system. “In communication” in the context of thedepicted device means that gas can flow between the chambers, elements,or devices being described as being “in communication.” The firstright-angle valve, #11, as with other components, can be opened orclosed manually, automatically, and/or under control of a computer,attached to the system, so as to practice the methods of the invention.In some cases, for example, the valve is closed to allow for controlledrelease of gasses from the sample container #1 into the rest of thesystem. The control afforded by inclusion of this first right-anglevalve, and other valve controls in the depicted system, can, forexample, permit different “runs” of the system on a single sample, underdifferent conditions, such as under the application of different vacuumpressures on the sample. Other types of valves, such as ball valves,in-line valves, or any other type of valve that can satisfactorilyoperate in a vacuum system (not shown) could be used instead ofright-angle valves as are exemplified here and described in any part ofthis disclosure.

Another two right-angle valves (#12 and #13) are connected to and incommunication with the first right-angle valve, #11, and respectivelycontrol the flow of dry nitrogen into the system and the flow of gasfrom the sample in container #1 into the liquid nitrogen trap container.Other purge gases such as dry air, argon, oxygen, helium, and othersalso or alternatively can be used as the purge gas instead of drynitrogen. Similarly, other cryogenic fluids such as liquid oxygen,liquid argon, liquid helium, and any other suitably cooling fluids alsoor alternatively could be used as the chilling means instead of liquidnitrogen exemplified here and described elsewhere herein.

The right-angle valve exterior is connected to a flexible vacuum hose,#14, which accommodates the up and down motion of the needle assemblyraising and lowering into various sample containers (#1, #2, #3) on thecarousel (#4). The vacuum hose #14 also is used to allow flow of gasesto create vacuum pressure and to also allow sample gasses to passfurther into the system. A pressure gauge #15 provides the operator withpressure conditions in the system, and thereby provides a check onwhether the system is operating as expected, which is important toensuring the validity of experiments and analyses performed in thesystem (other means/devices for measuring pressure also or alternativelycould be used). A fourth right-angle valve #16 controls access to adiffusion pump #16 a, (which typically are directly connected, asshown), which is used to expel gasses from the system (alternative meansand devices for pumping also or alternatively could be included in sucha system). A fifth right-angle valve, #17, provides a second inletcontrol on the liquid nitrogen trap container. As already mentioned allof these valves are controllable and control over the valves can beconfigured to operate in any suitable manner, so as to perform thevarious methods of the invention.

A relatively long first tube, #18, which is typically comprised ofaluminum or a similar material, provides communication between theright-angle valve #17 and the liquid nitrogen cooling chamber, #20,which also acts as the exterior of the liquid nitrogen trap componentsof the system. Along the tube #18, one or more heater(s), #19 a and #19b, can be placed, which allow for the application of heat, in arelatively predictable manner, to the system, which will aid with therelease of gasses frozen to the liquid nitrogen trap. The heaters can beany suitable type of heaters, including units that radiate heat, thatblow hot air, or that heat the tube by other suitable means. Typically,heaters (#19 a and #19 b) are placed at the ends of the first tube #18.

The liquid nitrogen cooling chamber #20 is the exterior of the liquidnitrogen trap freezing region. Here gas can come into contact with theliquid nitrogen cooled componentry of the system and freeze onto thetrap. The flow of liquid nitrogen is controlled by a liquid nitrogenvalve, #21. A thermocouple, #22, provides the user with the ability tomonitor the temperature of the system, and optionally can be configuredto send information to an associated computer system, which may controlcertain functions of the system. The liquid nitrogen trap has its owntemperature controller, #23, which helps in controlling the applicationof liquid nitrogen. A sixth right-angle valve, #24, is positioned at theexit of the liquid nitrogen trap region and controls the flow of gassesfrom the trap into the remainder of the system. A specializedright-angle valve, the release valve, #26, is a pin hole bypass foranalyzing gas that is released upon warming of the liquid nitrogen trapdue to operation of heaters, #19 a and #19 b. As described generallyabove, liquid nitrogen is applied to this region of the system, loweringthe temperature to a point at which volatile compounds contained in thesample can freeze to this trap region. The application of the heatersthen permits the release of the frozen gasses from the region to theremainder of the system, including the mass spectrometer, #31.

A pin hole apparatus, #25, is configured to regulate flow ofnon-condensable (noncondensable) gasses from the noncondensable gastrap, #27, into the mass spectrometer, #31. The noncondensable gas trap,#27, is configured to collect gasses that will not bind to the liquidnitrogen trap. The noncondensable gas trap #27 comprises a right-anglevalve, which allows for selective opening of this part of the apparatus,such that the gasses released from the warming of the liquid nitrogentrap are kept separate from the noncondensable gasses.

Diffusion pumps, #29 and #33, which may be backed by roughing pumps,provide flow and pressure control in the system, and are controlled byrespective valves, #28 and #32. Often, any other type or types ofsuitable high vacuum pump(s), such as turbomolecular or cryogenic pumpsor any other types of high vacuum pumps can be used instead of wherediffusion pumps are cited in any part of this application. Control viamanual operation or the computer system provides different amounts ofpressure (positive or negative) in all or parts of the system, throughthe operation of these pumps. As discussed above, in operation severalruns of the system can be performed on even a single sample by “pulling”on the sample through the application of different vacuum pressureconditions, thereby releasing different amounts of different gasses,thereby forming different aliquots from a single sample.

Access to the mass spectrometer, #31, is controlled by a massspectrometer valve, #30. Any suitable mass spectrometer can be used inthe system, and many are discussed above. The mass spectrometer #31 isconfigured to send information to a computerized system (not shown),typically via a data output connector (shown as wires connected to massspectrometer #31), indicating the presence of target compounds ofinterest, such as hydrocarbons, inorganic gasses, carbonic acid, aceticacid, or another organic acid, or the anticipated breakdown productsthereof, such as water or carbon monoxide.

Example 2

This example demonstrates the use of methods of the invention todetermine oil and water saturation in a formation based on analysis ofcuttings taken from an oil well, as well as permeability analysisobtained by analyzing a series of cuttings taken from the well.

Thirty samples of non-sealed cuttings taken from different depths in anoil well that had been stored in unsealed containers for a period ofapproximately three months under warehouse conditions in the summer(about 100-130 degrees F. estimated maximum daily temperature) weresubjected to analysis using a device as described in Example 1 toprovide information concerning the permeability of samples taken fromdifferent depths in the oil well, based on the release of targetsubstances. The cuttings were subject to two runs of the system, formingtwo aliquots, based on the application of pressure conditions of 50millibars and 5 millibars, respectively.

The right-hand column of FIG. 2, shown below, depicts an actual plot ofthe relative permeability of these samples, provided by two conventionalpermeability methods (e.g., the downward pointing triangles #1 areconventional sidewall oil core permeability measurements; curve #2represents permeability assessments made through conventional welllogging methods) and by application of the inventive method (upwardpointing triangles, #3), as applied to cuttings from an oil well site.This data represents one of the first times that permeabilityinformation from a site was obtained from oil well cuttings, and thedata shows that oil well cuttings can provide permeability informationwhich correlates well with data obtained from significantly moreexpensive traditional methods. The permeability data was plotted eitherin millidarcies or in relative proportion to other permeabilitymeasurements using conventional techniques.

Other information included in FIG. 2 is a plot of mud logging data (gaschromatography data), in the second column from the left, indicating thepresence of C1-C5 hydrocarbons in muds obtained from the respectiveplotted depths of the well (y axis).

The middle column provides S_(W) plots obtained from various methods(the continuous line, #4, represents data from conventional well loggingand the dots, #5, represent data taken from sidewall coring methods).The triangles, #6, are data obtained by the inventive method beingapplied directly to cuttings from the well. The results demonstrate astrong correlation in terms of Sw, here being obtained directly fromcuttings and also and from more conventional and often more expensiveconventional methods. This is another breakthrough aspect of theinvention, obtaining both permeability and S_(W) data from cuttings in asingle run and providing a comparative analysis of such data, fordifferent depths of a well, against other conventional methods ofassessing a well site.

Other information provided in FIG. 2 include the mud log resistivitycurve, data from oil staining on cuttings, caliper data (measuring borehole sizes, red dashed lines), and conventional gamma ray data (whichprovides information about the type of material at the site—such asshale versus sandstone, carbonate, etc.) (plots in the first column onthe left). Correlation of this information was used to identify thezones, which are indicative of the presence of oil, as marked by thevertical bar on the very left, #7. The water leg below the oil pay zoneis indicated by the lower vertical bar on the left, #8.

In this data, conventional resistivity data failed to convincinglyidentify the presence of oil that could be detected by the method of theinvention. This may be due to the inability of resistivity data todifferentiate between oil and gas, because both compounds arenon-conductive. This is one potential advantage of methods of theinvention exemplified by this example. The zone of the most abundant oilfluid inclusions was the water leg #8, not the oil pay zone #7. Thus,use of the previously described fluid inclusion methods on this wellalso failed to identify oil pay zones, which could be identified by thecutting methods of the invention, thereby also reflecting a benefit ofthe inventive method.

Example 3

This example demonstrates the identification of an oil pay zone, throughapplication of the inventive method on oil well cuttings, which weretaken from a section of an oil well that was not being prospected basedon application of pre-existing analytical methods.

Five hundred and eighteen cuttings taken from an oil well site, sealedat the well, were used in this analysis. Three aliquots were obtainedfrom each cutting, using pressure conditions similar to those describedin Example 2, plus an aliquot following intense sample dehydration.Permeability measures were obtained by the difference between aliquots 2and aliquot 1 for each cuttings sample, #1. The data from the analysiswere plotted and the actual plot of this data is shown in FIG. 3.

Numerous additional data points were also obtained and are reflected inFIG. 3, such as formic acid #2, acetic acid #3, oil saturated water #4,presence of C5-C10 paraffins #5, C6-C10 naphthenes #6, C6-C8 aromatics#7, and total oil #8. The gas components methane #9, ethane plus propaneplus butanes #10, and Total Gas #11 are also plotted, as is the sum ofthe oil and the gas #12. Oil and gas-indicating measurements wereobtained by the sum of the results of all three aliquots. The quality ofthe oil and gas product is indicated by the C8/(C5+C6+C7+C8) curve whichhelps differentiate heavier oil that plots to the right versus lighteroil and gas that plots to the left. The GOR (gas to oil ratio) curve #14helps determine gas prone versus oil prone zones. Theparaffins/(paraffins+naphthenes) curve #15, and thearomatics/(aromatics+naphthenes) curve #16 are used to evaluate thequality of the oil and discriminate various different oils from eachother.

This data reflects the identification of a discrete oil pay zone. Thelow permeability region #17 on the graph reflects a tight zone overlyingan accumulation. Below this tight zone (a zone of low permeability,generally less than about 10 millidarcies, and typically below about 1millidarcy) (a tight zone that overlies pay keeping it from migration inthe material can be considered a “seal”) (these terms are also subjectto general understanding in the art), two oil containing zones wereidentified through the assessment of the various basic data points. Theupper zone #18 had been missed by previously applied, conventionalmethods, but was identified through analysis of oil well cuttings, usingthe methods of the invention, whereas an actual oil producing zone #19was confirmed by the application of the various methods of the inventionon oil well cuttings.

A simplistic interpretation of this data is reflected in FIG. 3b , whichspecifically reflects and focuses on key signals in the permeability andoil saturated water data that characterize the geologic formation(material) studied in this Example. Specifically, the permeability datareveals a tight zone, #17, with little permeability, above a non-targetzone identified by oil saturate water according to the inventive methodemployed in this Example, #18, as well as the confirmation of a zoneidentified through other conventional methods, #19, through oilsaturated water analysis.

The concept of “oil saturated water” has been developed as part of theinvention described herein. “Oil saturated water” refers to water thathas chemical indications of fluid communication with oil. Specifically,samples indicative of containing oil saturated water refers to thosesamples that show relatively high amounts of the indicator compoundsformic acid, acetic acid, carbonic acid and/or bicarbonate, often fromthe presence of their breakdown indicator compounds, especially carbonmonoxide and/or water, or from a combination of detection of suchprimary and secondary indicators. Any of these conditions can becombined, such as, for example, methods of the invention can includedetermining the amount of water, one or more other inorganic gasses(e.g., one or more of hydrogen, helium, nitrogen, argon, oxygen,hydrogen sulfide, carbonyl sulfide, carbon disulfide, and/or sulfurdioxide), carbon monoxide, carbon dioxide, carbonic acid, acetic acid,formic acid, methane or other C1-C5 hydrocarbons, and/or bicarbonatethat is associated with/released from a sample as a means fordetermining if the same is associated with target substances, such asoil and/or natural gas. Conditions of analysis typically must be atleast partially controlled in order for water to provide an indicationof such material and, thus, communication with oil in a geologicformation. Thus, with respect to a device/system, such as thatexemplified in FIG. 1, and described above, water is advantageouslyreleased from the liquid nitrogen trap at a temperature colder than theusually water sublimation temperatures in the device/system, usuallyabout 55 degrees centigrade. Some of this water can then be detected atvery low liquid nitrogen trap temperatures, such as about −140 degreescentigrade. Water with high amounts of the indicator compounds can beconsidered oil saturated water, whereas water without these indicatorcompounds is not oil saturated water. This characterization of water ina formation cannot be made with conventional methods, especially inzones with very high water saturation, where conventional well logsessentially provide no information as to whether or not that specificwater is in communication with commercially viable oil and/or gasaccumulations. The determination of the presence of the indicatorcompounds by the inventive analytical methods provided here allows thisimportant distinction to be made. This tool can then be applied to wellsthat don't encounter commercially viable quantities of oil and/or gas,i.e., dry holes, to determine if such large commercially viable oil andgas occur close to the location of the dry hole, or not. These analysescould also be performed at the well site, and indicated zones of nearbyoil and gas could be targeted with side track wells drilled from theinitial pilot well at the fraction of the cost of drilling another wellto explore for the nearby pay zone at a later date.

This Example shows that cuttings-derived data, such as permeability andoil saturated water, can be used to determine the presence of oil and toalso determine permeability and discrete geologic zones containing oil,even ones missed by other, conventional methods.

Example 4

An analysis was performed as described in Examples 2 and 3 on 139cuttings that were sealed at the well or the deeper section of thevertical pilot oil well described in Example 3, other samples were takenfrom a lateral line drilled as a sidetrack from the pilot well followingthe evaluation of the pilot hole to locate the deep pay zone. Threealiquots were analyzed for each sample under the pressure conditionsdescribed above in Example 3. The oil saturated water results are shownin FIG. 4a (labeled element #1).

The oil saturated water anomaly in the vertical pilot well reveals anoil rich pay zone #2, which then became the target for drilling andfracking the lateral sidetrack. High water saturations are indicatedabove #3 and below #4 the oil pay zone #2. To be able to use thisinformation to aid in deciding at what depth to drill and land a lateralsidetrack to a pilot hole requires very quick analytical andinterpretive turnaround time. Usually the interpretation needs to bedelivered within 24 hours of the vertical pilot well reaching its totaldepth. Samples are often air expressed back to the lab, or hot shot bycar if close enough, once or twice a day so the analyses can keep upwith the drilling of the well as much as possible.

The oil saturated water data of the lateral sidetrack #5 shows thelateral was in the oil pay zone #2 penetrated by the vertical pilot wellfor about 2,700 feet, this is shown as #6. Following drilling in the oilpay zone #6 for about 2,700 feet the lateral sidetrack drilled through azone of low water saturation for about 1,000 feet #7. At the end of thelateral sidetrack, the oil pay zone was re-entered for about 500 feet#8. The lateral's well track #9 shows that the deepest part of thelateral was at the beginning of the lateral. The lateral continued todrill shallower and stay in the oil pay zone #6 until the bore holebecame sufficiently shallow that the lateral was no longer drilling inthe oil pay zone #6, but that further drilling was above the oil payzone and in the shallower water leg #7. Towards the end of drilling thelateral the well's track dips back down as shown towards the end of #9.Dipping back down results in the borehole re-entering the Oil Pay Zoneas #8, as revealed by the oil saturated water curve #5.

A stylized/simplified representation of certain elements of this data isprovided in FIG. 4b . Specifically, vertical zones of water #3, oil #2,and water #4 zones are plotted, with oil saturated water #15 along thewell track #9 identifying lateral zones of oil #6, water #7, and oil,#8. This reflects the ability of methods of the present invention to beapplied to wells that have both vertical and lateral characteristics,and to provide “maps” of data in both directions, even in a single wellor area.

This Example demonstrates that the methods of the invention can allowfor real-time data collection at the site of a lateral being drilled,such that this real-time data can be used to help “steer” (direct,guide) the direction of the lateral, so as to keep the borehole in orvery close to the oil pay zone.

Example 5

This Example demonstrates application of a method of this invention todistinguish between oil pay zones and gas zones in a well site.

In this Example, 205 sealed oil well cutting samples were subjected toanalysis as described above. Three aliquots were obtained from eachsample, under the discrete pressures (25 millibars, 1 millibars, and 0.1millibars)

SW was calculated from conventional petrophysical data, indicating thepresence of hydrocarbons in the geologic formation at the site. However,SW cannot distinguish between water and gas deposits, as discussedabove.

The results of the various data obtained by the performance of themethod, such as acetic acid and formic acid information, are plotted inFIG. 5. A stylized interpretation of this data is shown in FIG. 5B usingthe same numbering scheme as in FIG. 5.

A post-drilling appraisal of the target indicated the well underanalysis in this Example was a gas well and as such was not economic andwas abandoned. Conventional well logs indicated a large pay zone #1 ofseveral hundred feet in thickness overlain #2 and underlain #3 by stratahaving high water saturations. The well was perforated and tested atabout the middle depth of the pay zone. The well flowed gas. At thattime the operator abandoned the well thinking the pay zone was all gas.

Analyses using methods of the invention, however, indicates the bottom200 feet of the pay zone to be oil #7. This determination was based onhigh total oil responses #4, high acetic and formic acid responses #5,and high oil saturated water #6. The remaining pay zone above the oilpay is then gas #8, as tested. Above the gas are strata with high watersaturations #9, and below the oil pay are strata with high oilsaturations #10.

The data shown in FIGS. 5 and 5B demonstrates that cutting-derived dataobtained by applying methods of the invention can distinguish betweenoil and gas pay zones, which is of significant economic importance.

The data shown above demonstrates that cutting-derived data obtained byapplying methods of the invention can distinguish between oil and gasdeposits and also can confirm conventional core analysis information. Asconventional core analysis is significantly more expensive and more timeintensive than the cutting analysis of the invention this provides yetanother important benefit of the inventive methods.

Example 6

The methods of the invention can be applied to large regional areas orwells that span large regional areas to provide plots of entire fields,regions, or cross-regional wells. The identification of acetic acidand/or formic acid and/or oil saturated water in cuttings can indicatethat although that a subject well is a “dry hole” (a well not producingappreciable amounts of oil or gas), the well is nonetheless in proximityto a field. This data can then be used as a means for guidingexploration from the well site in terms of lateral drilling or thedrilling of new, nearby wells. A simple, stylized version of a plot ofdata that would be obtained from performing such an analysis is shown asFIG. 6.

More specifically, FIG. 6 provides a simplified 2-dimensionalrepresentation of a large conventional gas field. A permeable sandstonereservoir rock has undergone deformation so as to have a structuresuitable for trapping oil #1. The sandstone reservoir #1 is overlain bya shale having low permeability #2 that acts as a seal. Gas has migratedinto the sandstone reservoir #1 from a deeper source and now fills thesandstone down to the gas water contact (GWC) #3. The sandstoneshallower than the GWC is charged with gas. The pores in the sandstone,which are deeper than the GWC, are filled with water. Formic and aceticacids occur in oils and wet gases, and can partition out of the gas andoil phase into the water phase. These light carboxylic acids aremiscible in water. An aspect of the invention is the realization thatmeasurement of high amounts of these acids in formation waters inwater-filled permeable reservoir formations indicates close proximity tolarge economic pay zones in conventional oil and gas plays #6. Inunconventional reservoirs with very limited permeability the oil and gascoexist in intimate contact with high amounts of formation water, andoften in those cases the proximity to pay indicating acids occur in highamounts within the pay zone itself. This is the case in the previousExamples. However, in this conventional high permeability example, thegas and water are able to segregate into separate distinct zones ascontrolled by gravity separation.

Example 7

This Example provides the results of analysis performed with wetreservoir sands directly beneath two small local oil pay zones, as wellas two wet sand that are down dip from a giant gas reservoir, as shownin FIG. 7. The resistivity log indicates two small uneconomic pay zonesin this well, #2 and #3. Five rectangular boxes, #4 a-#4 e, are thesandstone bodies in this well as indicated by the gamma ray log. Therest of the penetrated strata depicted here are shales. Sands #4 a and#4 e have small oil legs at the top of the sands, and are water wetbelow the oil. Sands #4 c and #4 d are water wet, but are continuouswith reservoir sands to a giant gas field up dip. Sand #4 b is water wetand has no updip pay. The acetic acid information is plotted against aresistivity log. This data provides not only information about thepresence of oil pay zones, but mapped against the nature of the materialalso reflects where in the site would provide the best economic payout.

It can be advantageous to relate the methods and results of this Exampleto the disclosures in Example 6 and FIG. 6, in that the material of thisExample contains a thick water charged sandstone having row resistivityand being located about one half mile laterally and 500 feet in depthdown dip to a large gas field #1 that produces from the same sandstoneformation. There are no seals between the gas field and this dry hole.The sandstone, which is the source/cause of the dry hole, is in goodpermeable communication to the same sandstone formation in the giant gasaccumulation, as shown in FIG. 6.

Although this sand in fully water charged and shows low resistivity atthis location, the entire sandstone body shows high acetic acidcontents, which, according to an aspect of the invention, is indicativeof proximity to the giant nearby gas field #1 in FIG. 7. If this wellwas drilled prior to the nearby giant field being discovered, theconventional logs and other types of conventional analyses that mighthave previously ordinarily be applied to these samples, would haveprovided no indications that this well is in close proximity to thegiant gas field. However, the high acetic acid anomalies #1 in these wetsands #4 c and #4 d, provide a unique indication of the existence of alarge nearby petroleum accumulation. These data would strongly supportfurther exploration in this area.

There is another sand in FIG. 7 that is water wet and contains no pay #4b. The acetic acid contents of sand 4 b are similar to the surroundingshales above and below it. From other wells drilled in this area it wasknown that sand 4 b is not charged with gas or oil updip to thislocation. The low acetic acid contents of sand #4 b relative to theobviously higher acetic acid concentrations in zones #4 c and #4 dprovides a local calibration that indicates the importance of the aceticacid in sands #4 c and #4 d with respect to analyzing thecharacteristics of the material/formation.

There are two more sands #4 a and #4 e that the resistivity logindicates have small pay zones at the top of each sand. In each of thesesands with minor pay zones #4 a and #4 e, acetic acid anomalies #5 a forsand #4 a and #6 a for sand #4 e can be seen. A very interesting aspectof acetic acid anomalies #5 a and #6 a is that they also only occur nearthe top of each sand. The acetic acid anomaly for sand #4 c and #4 d ishigh for the entire sand body. This is the situation that was expectedfor a sand such as depicted in FIG. 6, wherein the entire sand body ischarged with oil or gas updip. Diffusion and fluid flow in geologicformations is usually much easier along bedding than across bedding.Hence the fact that the entire sands #4 c and #4 d show high acetic acidcontents is an indication that those sands are completely charged atsome distance updip, and they are. On the other hand, the fact thatsands #4 a and #4 e show acetic acid anomalies only at the top of thesands is an indication that this is a small oil deposit of only localextent and may be of lower or even insufficient economic interest withrespect to drilling. The acetic acid is observed only directly adjacentto the small oil columns seen in the resistivity log as #5 a and #6 a.Most of each #4 a and #4 e sand lacks any acetic acid anomaly as shownby the lower portions of each sand as #5 b and #6 b.

This data reflects that an aspect of the invention is the use of aceticacid data derived from geologic formations to classify the analyzedsands. Sand #4 b shows no increase in acetic acid relative to the shalesimmediately above and below, and therefore sand #4 b was determined tobe non-prospective, and data from surrounding wells support thatinterpretation. There are only very localized acetic acid anomalies atthe top of sands #4 a and #4 e, and this data indicates these aceticacid anomalies #5 a and #6 a are local in nature and not indicative ofnearby economically significant pay. On the other hand, the entirety ofsand #4 c and #4 d show high acetic acid contents. Even though themagnitude of the anomaly in sand #4 a is higher than that in sands #4 cand #4 d, the fact that the anomalies in #4 c and #4 d encompass theentire sand, whereas the anomalies in sands #4 a and #4 e encompass onlythe top of the sands is indicative that the #4 c and #4 d anomalies arerelated to/indicative of large and likely economically significant payzones, in contrast to the implications derived from the more limitedanomalies in sand #4 a and #4 e. Thus, this Example demonstrates how theinventive methods of the invention can be used to “map” or characterizean entire geologic structure or region with respect to proximity topetroleum pay zones in the structure/region.

Example 8

Plots were obtained from the performance of methods described above fora “dry gas” site and a “wet gas” site. The results of these analyses areshown in FIGS. 8A and 8B. A stylized interpretation of this data isshown in FIG. 8C. This analysis reflects the ability of methods of theinvention to distinguish between the nature of various target sites.

In FIG. 8a , a dry gas anomaly deep in the well is dominated by methane#1, ethane #2, and propane #3. Higher liquid hydrocarbons areessentially absent, with the exception of a trace amount of benzene #4that can be barely seen. The curve #5 shows the total amount of ethanethat would be produced from a standard lateral drilled about 4,500 feetlong with a production radius of about 50 feet. The analyst cancalculate this number as the number of nanomoles of the gases to beanalyzed can be determined as the results are quantitative andreferenced to analytical standards, and the volume of sample analyzed iskept constant to 400 microliters of rock for each sample. The resultshown as curve #5 is simply the result of upscaling the data to how muchethane by volume the analytical results are equivalent to for acylindrical rock volume that is 4,500 ft long with a radius of 50 ft.

FIG. #8B is plotted at the same scale as FIG. #8A. As shown, there ismuch less methane #1, ethane #2, and propane #3 here. Also, the datareflects there is much more liquid hydrocarbon content than seen in thedata of FIG. 8A. The C4-C8 paraffins are shown as #4-#8, the C6 to C8naphthenes are shown as #9-#11, and the C6-C8 aromatics are shown as#12-#14. The track showing predicted ethane production #15 isinsignificant compared to the same track #5 in FIG. 8A plotted at thesame scale. However, the predicted liquids production is much higher inFIG. 8B than in FIG. 8A. FIGS. 8A and 8B both depict unconventionalwells where the source rock is also the reservoir after hydraulicfracking. The source rock in the well shown in FIG. 8A has been buriedto much greater depths and thus has generated much drier gas than thesource rock in the well shown in FIG. 8B. The gas compositions derivedfrom these analyses thus provide information about burial history of thetarget formations, which is a critical piece of information in petroleumexploration, both for conventional and unconventional reserves.

This situation is shown in the simplified diagrams on FIG. 8C. The driergas shown as #1 is produced from the source rock that has experiencedmuch higher temperatures for much longer periods of time then the wettergas shown as #2.

These data can be used to address a great variety of geologic issues,especially when combined with other information from a variety ofsources.

Analysis can be and often will be applied to relatively greater sizedhydrocarbons, such as up to C10 hydrocarbons, but the C9 and C10 dataobtained in this work were omitted from the FIGS. 8a and 8b for the sakeof clarity. Since FIGS. 8A and 8B are plotted at the same scales, it isapparent that the gas from the FIG. 8A well is much drier than the gasfrom the FIG. 8B well. This Example reflects several aspects of theinvention—from making standards to using such standards or moregenerally comparing data from several well sites to characterize amulti-well geographic/geological area.

Example 9

Methods of the invention could be applied to map out regions, as notedelsewhere herein. An illustration of the concept is shown as FIG. 9.FIG. 9 provides an example of what the output of such a regional mappingof oil well sites would conceptually look like, providing areas of highoil indications #1 and/or other information, such as porosity, whichcould be used to provide maps of favorable drilling sites and also usedto predict other less prospective sites versus zones of low oilindications #2 or zones of low proximity to pay indications, or otherindications from the data that can attest to high or low probability offinding oil and/or gas.

Example 10

In this Example, data was gathered in a manner similar to the protocolsdescribed in Examples 2-4. The data obtained from this analysis is shownas FIG. 10 and an interpretation of the data is provided as FIG. 10A.

The well depicted in FIG. 10 was drilled for a deeper target and therewas no effort expended in searching for pay zones in the shallower partof the well depicted in FIG. 10. However, analyses of samples shown inFIG. 10 revealed a 600-foot oil column that was indicated by high oilsaturated water #1 and high formic and acetic acids #2. As discussedabove, in unconventional reservoirs having very low permeability, one ormore proximity to pay indicators, e.g., formic and acetic acids, candelineate the pay zone in as much as the water and oil coexist in thesame strata in an unconventional reservoir, and do not separate out intodiscrete oil pay zones versus water legs as happens in much morepermeable conventional reservoir settings.

The 600-foot oil column detected by oil saturated water #1 and organicacids #2 is actually two oil accumulations that are juxtaposed one ontop of the other. Analysis of the data allows for discrimination ofthese two oils as having different chemical compositions using theparaffins/(paraffins+naphthenes) and thearomatics/(aromatics+naphthenes) curves #3, with relatively low valuesfor both these ratios in the upper 400 feet of the pay zone #3 that wasidentified defined using oil saturated water #1, and organic acids #2.However, data #4 shows high values for both of these ratios for thedeepest 200 feet of this pay zone. The data indicate to those skilled inthe art that the oil in upper zone #3 is heavier than the oil in thelower zone #4. This is somewhat unusual if this were a conventional oiland gas reservoir system, as in those systems oil and gas becomestratified by gravity according to density, that is to say inconventional reservoirs petroleum is usually stratified with the lighterpetroleum above the heavier petroleum. This, however, is not a trendthat has particular relevance in unconventional reservoirs withvanishingly small permeabilities. In this case, the data obtained by theinventive method indicates that the #3 reservoir is a tight carbonateinto which oil and gas have migrated into from some source rock that isspatially removed from the reservoir. Reservoir #4 in contrast is anorganic-rich shale that is both the source for the oil it holds, and thereservoir for the oil. Unconventional oil from source rocks tends to belighter than migrated oil. Migrated oil tends to lose lighterhydrocarbons during expulsion from the source rock, i.e., primarymigration, and transport to the reservoir, i.e., secondary migration,and during the residence of the petroleum in the reservoir. As tightshales can be both source and reservoir, the oil in tight shales doesnot lose its more volatile components during migration and while beingin the reservoir, and hence is usually lighter than conventional oil.Hence it is reasonable to conclude that the overlying oil #3 in a tightlimestone is heavier than the underlying oil in a tight organic-richshale.

From a production point of view reservoir #3 and reservoir #4 will needto be produced as separate reservoirs. Reservoirs #3 and #4 are not incommunication. They will produce different types of oil. And variousaspects of the reservoir, such as fluid pressure, will be different.This reflects an advantageous element of the invention in identifyingand characterizing separated pay zones of separate characteristics.

FIG. 10A illustrates other aspects of this Example. Curve #1 on the leftis the resistivity curve that indicates a 600-foot oil column overlainand underlain by water, as shown by the product type log #2. The600-foot oil column #1 is shown to be divided into a 400-foot-thickupper heavier oil reservoir and a deeper 200-foot-thick lighter oilreservoir #4. The distinction between shallow heavy oil reservoir #3 anddeeper lighter oil reservoir #4 is based on the paraffins/naphthenesratio curve #5 and the aromatics/naphthenes ratio curve #6.

The results of this analysis demonstrate that methods of the inventionas exemplified here can identify two separate oil pay zones, and furtherdemonstrate that the cutting analysis methods of the invention can beused to distinguish between different types of oil pay zones in a wellsite, which might otherwise be confused with one another based on othermethods of analysis.

Example 11

Methods of the invention can be performed to demonstrate different oilpay zones at a site due to the presence of different profiles ofhydrocarbons present in the respective sites. In this respect, themethods of the invention could be used to identify compartmentalized anddiscrete oil pay zone sites. A reflection of this concept is provided inFIG. 11.

As shown in FIG. 11, Well A #1 and Well B #2 are both oil wells drilledin similar geologic situations. The oil pay zone in Well A #3 is oilcomprised of high paraffins and aromatics content, but low naphthenescontent. The oil pay zone in Well B #4 contains oil comprised of highparaffins and aromatics content, but also high naphthenes content. Theoil in reservoir #3 will have a different character from the oil inreservoir #4. Documenting the difference using data obtained by theinventive methods described herein will then allow those trained in theart of oil exploration to consider various scenarios to account for thisobserved difference. Also, the knowledge that two different oilsoccurring in one area reduces exploration risk in that area as theprobability of finding oil is increased if there is more than one oilsource that can charge reservoirs in the area being explored.

Example 12

This Example provides an illustration of a method for the measurement ofmany of the above-described parameters associated with a sample forcharacterizing a material in a well site device according to certainaspects of the invention, where the inventive method involving the useof the device occurs while the well is drilling at such a rate so thatthe data are obtained as quickly as possible so that those data can beused to help “steer” the well in a close to “real time” manner (it isexpected that there may often be a “lag” of about 10-100, such as about20-60 feet, from the location of the active drill and the latestlocation of data analysis, simply given the logistics of welloperations, such as limitations of what can be placed at a drill bit,interfering noise and motion, etc.). Aspects of the invention such asthe device and method envisioned here can be advantageous for theoptimum placement of lateral wells, also known as horizontal wells.

A device for a rapid method for determining frackability on the wellsite is depicted in FIG. 12. With reference to the device of FIG. 12, #1depicts the discharge of mud and cuttings from the flow line and intothe possum belly of a conventional oil well. A reusable collapsiblecontainer, #2, is positioned so that a portion of the mud and cuttingsdischarge must flow through it. A screen, #4, is placed at the bottom ofreusable collapsible container, #2, that allows drilling mud to escapethe reusable collapsible container #2, but retains the cuttings #3inside the container. An air piston, #5, is situated outside of the mudand cuttings discharge #1. The air piston #5 transmits unidirectionalforce for crushing the cuttings #3 through the elongate rod #6. Arotating device, #7, usually driven by air pressure rotates the screen#4 using rod #8 away from the collapsible container #2 to dischargematerial from the cuttings #3 after they have been crushed. The screen#4 is retracted from the reusable collapsible container #2 for asufficient amount of time to allow the now crushed cuttings #3 to beremoved from the reusable collapsible chamber #2 to be cleansed from thechamber by the vigorous flow of mud and cuttings #1. The device #7 couldbe another air piston that moves the screen laterally out from underreusable collapsible container #2 instead of a rotating device.

The top view shows the reusable collapsible container #2 is comprised oftwo parts. Part #9 is U-shaped in cross section having two right anglecorners. The fourth wall of the reusable collapsible container is aplate #10 that has no solid connection with part #9 of the container.Upon filling of the reusable collapsible container #9 and #2 withcuttings #3 from the flow line mud and cuttings discharge #1, thecuttings are crushed by activating air piston #1 to squeeze them throughtransmitting a force through rod #11 to the plate #10. The frackabilityof the cuttings is determined by measuring and recording how much therod #11 has been extended out from the air piston #12. The speed andfluidity of motion of the crushing of the cuttings #3 can also berecorded, as can any recovery of the crushing assembly upon release offorce on air piston #12. These parameters can aid in a more completedescription of the mechanical properties of the cuttings, includingPoisson's Ratio, and Young's modulus. These parameters, along withfrackability, can be important and useful in steering a lateral to stayin the rocks of optimum mechanical strength, and in determining the bestmanner in which to complete the lateral through the fracking andproduction stages of oil production.

List of Illustrative Aspects of the Invention

The following is a non-limiting list of certain aspects of the inventionthat can provide additional assistance and guidance in understanding theunique features and advantages that the invention provides.

The first set of aspects relates to methods in which multiple aliquotsare obtained from a sample and the volatile substances in such aliquotsanalyzed:

-   -   1. A method for analyzing volatile substances in a material        comprising:—        -   a. Providing an analyzable sample of a material        -   b. Subjecting the sample to one or more forces to release a            first gas containing an analyzable amount of one or more            volatile substances,        -   c. Trapping and concentrating the first gas in or with a            media in an analyzable amount to generate an aliquot,        -   d. Isolating the aliquot from the sample,        -   e. Releasing volatile substances from the aliquot as            released gasses in a predictable sequence,        -   f. Analyzing the volatile substance chemistry of at least            one of the volatile substances to obtain an analysis of the            aliquot,        -   g. Performing at least one more cycle of analysis comprising            repeating steps b-f of the method, at least one additional            time, wherein for each repetition the specific force applied            is distinct from the force previously applied to the sample,            and        -   h. Analyzing all of the analyses to provide information            about the material.    -   2. The method of aspect 1, wherein the one or more forces        comprises subjecting the sample to a specific pressure without        mechanical disruption, e.g., crushing.    -   3. The method of aspect 2, wherein the sample is initially        subjected to the specific pressure at which it was sealed in its        container so as no unsealed volatiles are lost. This is usually        performed at about 1-100 millibars, such 2-80 millibars, e.g.,        about 3-75 millibars.    -   4. The method of any one of aspects 1-3, wherein the sample is        subjected to the specific pressure and temperature at which it        was initially obtained.    -   5. The method of any one of aspect 4, wherein the method        comprises subjecting the sample to different pressures, without        mechanical disruption.    -   6. The method of any one of aspects 1-5, wherein the analysis of        the volatile substance chemistry comprises subjecting the        volatile substances to mass spectrometry.    -   7. The method of any one of aspects 1-6, wherein the analysis        provides information concerning the quantity of one or more        volatile compounds in the material.    -   8. The method of any one of aspects 1-7, wherein step h of the        method (the analysis step) comprises comparing at least some of        the analyses against one or more standards.    -   9. The method of any one of aspects 1-8, wherein the force        comprises dehydrating the sample prior to crushing, applying        mechanical pressure on the sample, mechanically rupturing some        or all of the sample, subjecting the sample to a chemical        reaction, or a combination of any thereof.    -   10. The method of any one of aspects 1-9, wherein the method        further comprises subjecting the sample to two or more different        pressures, optionally to generate two or more aliquots.    -   11. The method of any one of aspects 1-10, wherein the volatile        substances comprise C1-C20 hydrocarbons.    -   12. The method of any one of aspects 1-11, wherein the step of        trapping comprises subjecting the gas to a non-selective trap.    -   13. The method of any one of aspects 1-12, wherein the step of        trapping comprises cryogenic capture of the gas.    -   14. The method of aspect 13, wherein the trapping step comprises        subjecting the gas to temperatures of less than about −50        degrees C.    -   15. The method of aspect 14, wherein the method comprises        contacting the gas to a material cooled by contact with liquid        nitrogen.    -   16. The method of any one of aspects 1-15, wherein the volatile        substances comprise C1-C10 hydrocarbons.    -   17. The method of any one of aspects 3-16, wherein the pressure        is either ambient atmospheric pressure positive pressure in        excess of ambient atmospheric pressure, or a level of vacuum        below atmospheric pressure but greater than 3×10⁻⁴ millibars.    -   18. The method of aspect 17, wherein the pressures applied to        the sample are greater than 1×10⁻³ millibars.    -   19. The method of aspect 18, wherein the pressures applied to        the sample are greater than 25×10⁻³ millibars.    -   20. The method of aspect 19, wherein the pressures applied to        the sample are greater than 1×10⁻² millibars.    -   21. The method of any one of aspects 3-20, wherein the method        comprises subjecting the sample to a pressure of between 1-100        millibars.    -   22. The method of any one of aspects 1-21, wherein the sample is        a rock that comprises no recent fluid inclusions that could have        trapped recent fluids such as present day oil and/or gas.    -   23. The method of aspect 22, wherein the sample has not        experienced significant burial diagenesis.    -   24. The method of any one of aspects 1-23, wherein the method        comprises removing potentially interfering gasses from contact        with the media prior to analyzing gasses released from the        aliquot.    -   25. The method of aspect 24, wherein the interfering gasses        removed comprise oxygen, nitrogen, or both oxygen and nitrogen.    -   26. The method of aspect 25, wherein the method comprises        purging oxygen and nitrogen from contact with the media by        contact with an inert gas that does not chemically react with        the sample and does not cause any interferences with the        chemical analyses of the samples' volatiles.    -   27. The method of aspect 26, wherein the inert gas is an inert        gas, such as argon or nitrogen.    -   28. The method of any one of aspects 1-27, wherein more than 50%        of the volatile substances in the sample are analyzed by the        method.    -   29. The method of aspect 28, wherein more than 75% of the        volatile substances in the sample are analyzed by the method.    -   30. The method of aspect 30, wherein more than 90% of the        volatile substances in the sample are analyzed by the method.    -   31. The method of aspect 30, wherein more than 99% of the        volatile substances in the sample are analyzed.    -   32. The method of any one of aspects 1-31, wherein the first gas        is allowed to contact the media for 0.1 seconds to 10 minutes.    -   33. The method of any one of aspects 1-32, wherein the first gas        is allowed to contact the media for about 10 minutes or longer.    -   34. The method of aspect 33, wherein the first gas is allowed to        contact the media for about 20 minutes or longer.    -   35. The method of aspect 34, wherein the first gas is allowed to        contact the media for about 40 minutes or longer.    -   36. The method of any one of aspects 1-35, wherein the method        does not comprise heating the sample to temperatures greater        than 100° C.    -   37. The method of aspect 36, wherein the method does not        comprise heating the sample to temperatures greater than 60° C.    -   38. The method of any one of aspects 1-37, wherein the method        comprises collecting a portion of the first gas of at least one        of the cycles that will not bind to the media as a separate        non-condensable gas and subjecting this non-condensable gas        aliquot to a separate analysis.    -   39. The method of aspect 38, wherein the media is a cooled        surface to which the first gas condenses and at least some of        the portion will not condense on the cooled surface.    -   40. The method of aspect 38 or aspect 39, wherein the method        comprises isolating the non-condensable gas from the condensable        gasses to facilitate separate analysis thereof.    -   41. The method of any one of aspects 38-40, wherein the portion        of the non-condensable gas comprises methane, helium, hydrogen,        or a combination of some or all thereof.    -   42. The method of any one of aspects 38-41, wherein the portion        of the non-condensable gas comprise neon, argon, krypton, or a        combination of two or more of these gasses.    -   43. The method of any one of aspects 1-42, wherein the method        comprises containing the sample in a container which isolates        the sample from the environment in a manner that substantially        retains volatile substances in the sample from the time the        sample is placed in the container until release of the first        gas.    -   44. The method of aspect 43, wherein the container comprises a        seal that can be selectively punctured to release the first gas        allowing gaseous contents of the container to flow into contact        with the media when punctured.    -   45. The method of aspect 43, wherein the container comprises a        puncture-free connector system.    -   46. The method of any one of aspects 1-45, wherein the method        comprises collecting the first gas under each different        condition for at least about 1 minute to form each aliquot.    -   47. The method of any one of aspects 1-46, wherein the method        comprises the step of substantially removing one or more        potentially interfering gasses before trapping the first gas.    -   48. The method of aspect 47, wherein the step of removing        potentially interfering gasses is completed in about 3 seconds        or less.    -   49. The method of aspect 47 or aspect 48, wherein the        potentially interfering gasses comprise oxygen, nitrogen, carbon        dioxide, or a combination thereof.    -   50. The method of aspect 47 or aspect 49, wherein the method        comprises purging the potentially interfering gas from contact        with the media by filling the area surrounding the media with a        purging gas, such as a non-condensable gas.    -   51. The method of aspect 50, wherein the purging gas is argon or        krypton.    -   52. The method of any one of aspects 1-51, wherein the media is        a cooled surface.    -   53. The method of aspect 52, wherein the surface is cooled by        indirect contact with liquid nitrogen, or another cryogenic        liquid such as liquid argon, liquid oxygen, or liquid helium.    -   54. The method of any one of aspects 1-53, wherein the method        comprises performing an optional analysis at atmospheric        pressure and at least two analyses at different pressures both        of which are below atmospheric pressure.    -   55. The method of any one of aspects 1-54, wherein the method        does not comprise performing gas chromatographic analysis.    -   56. The method of any one of aspects 1-55, wherein the method        comprises evaluating the permeability of the sample by assessing        differences in the aliquots obtained by extraction under two        different sets of conditions.

The following listing of aspects of the invention is directed to amethod of the invention comprising extracting and analyzing only asingle aliquot of material:

-   -   57. A method for analyzing volatile substances in a material        comprising:        -   a. Providing an analyzable sample of a material        -   b. Subjecting the sample to one or more forces to release a            first gas containing an analyzable amount of one or more            volatile substances,        -   c. Trapping and concentrating the first trappable gas (such            as a condensable gas in a system that relies on condensation            of the gas) in or with a media in an analyzable amount to            generate an aliquot,        -   d. Isolating the aliquot from the sample,        -   e. Releasing volatile substances from the aliquot as            released gasses in a predictable sequence, and        -   f. Analyzing the volatile substance chemistry of at least            one of the volatile substances to obtain an analysis of the            aliquot.    -   58. The method of aspect 57, wherein the method comprises only        forming and analyzing a single aliquot, which may comprise two        or more sub-aliquots.    -   59. The method of aspect 58, wherein the single aliquot        comprises a condensable gas component that is trapped with a        first trap and a non-condensable gas component that is        separately collected.    -   60. The method of any one of aspects 57-59, wherein the method        comprises subjecting the sample to at least one pressure of at        least 1 millibar and less than 1 atmosphere.    -   61. The method of aspect 60, wherein the method comprises        subjecting the sample to a pressure of about 1 millibar to about        100 millibars.    -   62. The method of any one of aspects 57-61, wherein the sample        is subjected to vacuum pressure for a period of about 0.25        minutes to about 15 minutes.    -   63. The method of any of aspects 57-62, wherein the one or more        forces comprises subjecting the sample to a crushing force in        addition to one or more other forces such as vacuum pressure,        vibrational energy, or radiation energy, such as laser        excitation, or a combination of any or all thereof.    -   64. The method of any one of aspects 57-63, wherein the analysis        of the volatile substance chemistry comprises subjecting the        volatile substances to mass spectrometry or other method of        analysis.    -   65. The method of any one of aspects 57-63, wherein the step of        trapping comprises cryogenic capture of condensable gas and        optionally capturing a sub-aliquot of non-condensable gas in a        separate manner for separate analysis.    -   66. The method of any one of aspects 57-65, wherein the method        comprises removing potentially interfering gasses from contact        with the media prior to analyzing gasses released from the        aliquot.    -   67. The method of any one of aspects 57-66, wherein the method        does not comprise heating the sample to temperatures greater        than 100° C.    -   68. The method of any one of aspects 57-67, wherein the method        comprises measuring the ductility of the sample by providing the        sample in a crushable container and determining the size of the        impact of the crushing force on the container and sample.    -   69. The method of any one of aspects 57-68, wherein the method        comprises collecting and sealing samples at the wells versus        loaded in lab samples.    -   70. The method of any one of aspects 57-69, wherein the method        comprises collecting and analyzing samples in close proximity to        the well site.    -   71. The method of any one of aspects 57-70, wherein the method        comprises collecting and analyzing samples inside a well, such        as a well that is under active drilling.    -   72. The method of aspect 71, wherein the method comprises        real-time or near real-time analysis of samples, for example        where the lag time between the site of drilling and the analysis        of samples is less than about 50 feet, such as less than about        40 feet, less than about 30 feet, less than about 20 feet, or        less than about 10 feet, 7 feet, 5 feet, or even less than about        1 foot.    -   73. The method of any one of aspects 57-72, wherein the method        comprises measuring the amount of acetic acid, formic acid,        and/or oil saturated water associated with the sample.    -   74. The method of any one of aspects 57-73, wherein the method        comprises measuring the amount of methane, carbon dioxide,        and/or carbon monoxide that is released from the trap.    -   75. The method aspect 74, wherein the method comprises measuring        the amount of carbon monoxide that is released from the trap.    -   76. The method of any one of aspects 57-75, wherein one or more        steps of the method are performed in close proximity to a        petroleum well site.    -   77. The method of aspect 76, wherein the method is performed        within about 150 feet of the site of drilling.    -   78. The method of aspect 77, wherein the method comprises        pneumatic delivery of samples to a laboratory for analysis.    -   79. The method of aspect 78, wherein the method comprises        analysis in real-time while the well is drilling and the data is        used to steer the well to keep the borehole in or as close as        possible to the target pay zone.

In general, the aspects that are dependent on aspect 57 can apply to themethod of aspect 1. The aspects that are dependent on aspect 1 can beapplied to aspect 57. In fact, aspect 1 can be considered to depend fromaspect 57. Any of these methods reflected in aspects 1-79 can comprisedeveloping a standard and/or adjusting for conditions at a location(e.g., calculating carbon monoxide located at a location andsubstracting it from a measured amount, or applying a similar approachto formic acid, acetic acid, and/or oil saturated water).

The following set of aspects is directed to a method focused onprimarily assessing ductility (frackability) of a material byperformance of a method of the invention:

-   -   80. A method for analyzing the ductility or hardness of geologic        formation comprising:        -   a. Providing an analyzable sample of a material,        -   b. Subjecting the sample to one or more forces that are            capable of compressing material of a given hardness or            ductility, and        -   c. Determining the amount of compression of the sample.    -   81. The method aspect 80, wherein the method comprises        compressing multiple sides of the sample contemporaneously.    -   82. The method of aspect 81, wherein the method comprises        isotopically compressing the sample.    -   83. The method of any one of aspects 80-82, wherein the sample        is obtained from a petroleum well.    -   84. The method of aspect 83, wherein the sample is selected from        a cutting and a core sample.    -   85. The method of aspect 84, wherein the sample is a cutting.    -   86. The method of any one of aspects 80-85, wherein the method        is performed on multiple samples from a site.    -   87. The method of aspect 86, wherein the samples comprise        samples obtained from different depths of a material wherein the        depths range from about 0.5 feet to about 100 feet.    -   88. The method of aspect 86 or aspect 87, wherein the samples        comprise materials obtained from the same approximately the same        zone of depth but from locations that are separated by about 0.5        feet to 100 feet.    -   89. The method of any one of aspects 86-88, wherein the method        comprises analyzing at least 10 samples from different depths.    -   90. The method of any one of aspects 86-89, wherein the method        comprises analyzing at least 10 samples from the same zone of        depth.    -   91. The method of any one of aspects 86-90, wherein the method        comprises analyzing about 10 to about 2,500 samples.    -   92. The method of any one of aspects 80-91, wherein the method        comprises combining the results of the method with the results        of mineralogic analysis of the sample, other samples, or the        material, x-ray diffraction of the samples, other samples or the        material; x-ray fluorescence of the samples, other samples, or        the material; a total organic content measurement associated        with the samples, other samples, or the material, and/or        combination with other data such as photography and/or        spectroscopy of the samples or other samples or the material by        any suitable means in any wavelength, and/or chemical,        geochemical, or material testing of the samples, related        samples, or the material, or a combination of any or all        thereof.

The following set of aspects are directed to a device of the inventionfor the analysis of oil saturation and/or water saturation from samples:

-   -   93. A device comprising:        -   (a) a chamber for receiving and isolating samples of a            material        -   (b) a detection component capable of detecting the amount of            one or more target volatile substances released from the            sample, wherein the substance comprises carbon monoxide,            acetic acid, formic acid, or a combination thereof,            optionally in combination with hydrocarbons, inorganic            gasses, or a combination thereof.    -   94. The device of aspect 93, wherein the device comprises an        energy input component that promotes the release of volatile        substances from the sample.    -   95. The device of aspect 94, wherein the energy input component        is (a) a pressure generating device or system, (b) a device or        system that promotes release of volatile substances through        mechanical forces, thermal forces, or both, or a combination        of (a) and (b).    -   96. The device of any one of aspects 93-95, wherein the device        comprises a system or component for isolating volatile        substances released from the sample.    -   97. The device of any one of aspects 93-96, wherein the device        comprises a trap for collection and release of volatile        substances.    -   98. The device of aspect 97, wherein the trap comprises a        non-selective trap, such as a trap that comprises a liquid        nitrogen trap.    -   99. The device of any one of aspects 93-98, wherein the device        comprises a mass spectrometer.    -   100. The device of any one of aspects 93-99, wherein the device        comprises a component or device for selectively isolating the        mass spectrometer from the sample.    -   101. The device of aspect 100, wherein the device comprises a        volatile substance trap and the method comprises a component or        device for selectively isolating the volatile substance trap        from the sample, the mass spectrometer, or both.    -   102. The device of any one of aspects 93-101, wherein the device        is part of a system that comprises a mechanism for determining        the compressibility of the sample.

The following set of aspects are directed to another type of deviceprovided by the invention:

-   -   103. A device for chemical analysis comprising: (a) a cryogenic        trap, (b) a cooling component for selectively cooling the        cryogenic trap, (c) a warming component for selectively warming        the cryogenic trap, and (d) an analytical device comprising a        mass spectrometer for analyzing one or more volatile substance        released from the cryogenic trap.    -   104. The device of aspect 103, wherein the warming component is        operable in a manner that provides for controlled warming of the        cryogenic trap to promote separate release of two or more        amounts of volatile substances from the cryogenic trap.    -   105. The device of aspect 103 or aspect 104, wherein the device        further comprises a vacuum that can promote the release of        volatile substances from a material in communication with the        device, wherein at least one of the volatile substances can be        trapped on the trap.    -   106. The device of any one of aspects 103-105, wherein the        device comprises one or more housing components that keep at        least an analyzable proportion of the volatile substances        captured by the trap separate from the environment.    -   107. The device of any one of aspects 103-106, wherein the        device further comprises a component for promoting the flow of        substances through the device, such as one or more selectively        operable pumps.    -   108. The device of any one of aspects 103-107, wherein the        device comprises a component or system for capturing one or more        substances that do not bind to the cryogenic trap and for        separately analyzing such one or more non-binding substances.    -   109. The device of any one of aspects 103-108, wherein the        device comprises components for delivering a cryogenic substance        selected from the group consisting of liquid nitrogen, liquid        argon, liquid oxygen, liquid air, liquid helium, dry ice, a dry        ice slurry, normal ice, a normal ice slurry of water ice in        fresh water, a normal ice slurry of water ice in a saline brine,        or any other naturally cooling substance capable of achieving        the minimum temperature required to freeze the substance(s) of        interest onto the cryogenic trap.    -   110. The device of any one of aspects 103-109, where the        cryogenic state of the trap is at least partially achieved, and        the device comprises components for mechanical refrigeration or        cooling, as may be achieved with, e.g., a Kelvinator device. The        Kelvinator or other cryogenic device must be able to achieve the        minimum temperature required to freeze the substance(s) of        interest onto the cryogenic trap.    -   111. The device of any one of aspects 103-110, where the device        further comprises an additional mass spectrometer, a gas        chromatograph; an infrared spectrometer; a Raman spectrometer;        or any combination of these analytical devices.

In another aspect of the invention, the methods, systems, and devicesdescribed above further comprise components for or steps for determiningthe permeability of a sample, through application of two differentforces, such as two different pressures, to each sample analyzed forpermeability, and analyzing the difference in the release of one or moresubstances or substance classes, such as hexanes, upon the applicationof the different forces. Any one of the above described 102 aspects canbe further modified by addition of such step or the inclusion ofsettings or components for practicing such steps.

Incorporation by Reference and Interpretation

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

The invention claimed is:
 1. A method for analyzing the mechanicalstrength of a geologic formation comprising: a. Placing a plurality ofseparated samples of material obtained from the geologic formation intoa container, the container comprising a top, bottom, and two or moresides, b. Subjecting the container to one or more compression forces,wherein at least one of the one or more compression forces are appliedto at least two sides of each container, and the samples interact withat least two sides of the container, c. Determining the amount ofcompression of the container, and d. Assessing the mechanical strengthof the geologic formation by evaluating the compression of the containercomprising the samples.
 2. The method of claim 1, wherein the methodcomprises collecting groups of samples, each group of samplesoriginating from different portions of a petroleum well, and the methodcomprises using the mechanical strength of the different groups ofsamples to predict the post-fracking oil production capabilities of theformation.
 3. The method of claim 1, wherein the samples do not fill theentirety of the container such that the container further comprises airwhen step (b) of the method is performed.
 4. The method of claim 3,wherein the samples are under a pressure of between 1 millibar and 1atmosphere when the one or more compression forces are applied to thecontainer.
 5. The method of claim 4, wherein the samples comprise one ormore cuttings from a well drilling operation, the cuttings comprisingone or more volatile compounds that are not located in fluid inclusions,and the majority of the volatile compounds are not released from thecontainer before or during the step of subjecting the container to oneor more compression forces.
 6. The method of claim 5, wherein the one ormore compression forces comprises mechanically crushing two or moresides of each container used in the method.
 7. The method of claim 6,wherein the method comprises penetrating the top of the container, thebottom of the container, or both, with a penetrating device thatselectively allows gas comprising the volatile compounds to flow out ofthe container.
 8. The method of claim 7, wherein the method comprisesproviding two or more collections of samples each collection of samplesbeing collected from different areas of the geologic formation and eachcollection is placed in a separate container, the method furthercomprising performing steps a-d of the method separately on eachcontainer and the collection of samples contained therein.
 9. The methodof claim 8, wherein the method is performed on at least 10 containerseach container containing a collection of samples obtained fromdifferent portions of the geologic formation.
 10. The method of claim 7,wherein the one or more compression forces is applied by contacting atleast one side of the container with an object comprising a first hardsurface to compress at least one other side of the container against asecond hard surface.
 11. The method of claim 7, wherein the methodfurther comprises e. Subjecting the samples to one or more gas-releasingforces to release a first released gas containing an analyzable amountof one or more volatile substances, f. Trapping and concentrating thefirst released gas in or with a media in an analyzable amount togenerate an aliquot, g. Isolating the aliquot from the sample, h.Releasing volatile substances from the aliquot as released gasses, andi. Detecting and analyzing the volatile substance chemistry of at leastone of the volatile substances to generate an analysis of the aliquot.12. The method of claim 11, wherein the one or more gas-releasing forcescomprise applying pressure on the samples that causes the release of oneor more volatile substances in samples, including volatile substancesnot contained in fluid inclusions, and the method further comprisesassessing the amount of one or more volatile substances released fromthe samples after application of the pressure.
 13. The method of claim11, wherein the first released gas further comprises a non-condensablegas portion that comprises one or more volatile substances that do notbind to the media and that is captured separately from the portion ofthe released gas that binds to the media sub-aliquot and is separatelyanalyzed with a second analysis.
 14. The method of claim 13, whereinstep (e) of the method comprises subjecting the samples to at least onepressure of at least 1 millibar and less than 1 atmosphere.
 15. Themethod of claim 14, wherein the method comprises subjecting the samplesto a pressure of 1 millibar to 100 millibars.
 16. The method of claim15, wherein the samples are subjected to vacuum pressure for a period of0.25 minutes to 15 minutes.
 17. The method of claim 16, wherein step (i)of the method comprises subjecting the volatile substances to massspectrometry analysis.
 18. The method of claim 11, wherein the methodfurther comprises measuring the amount of one or more compounds selectedfrom the group consisting of formic acid, acetic acid, carbonic acid,bicarbonate, one or more C1-C15 hydrocarbons, hydrogen, helium,nitrogen, argon, oxygen, hydrogen sulfide, carbonyl sulfide, carbondisulfide, sulfur dioxide, carbon monoxide, carbon dioxide, or water,which are released from the samples and detected in step (e) of themethod.
 19. The method of claim 11, wherein the method comprisesmeasuring the amount of formic acid, acetic acid, carbonic acid, carbonmonoxide, carbon dioxide, or water detected in step (i) of the method.